Gergely Pl - Penke Botond - Tth Gyula

Szerves
s bioorganikus
kmia
egyetemi tanknyv
harmadik, tdolgozott kiads

Semmelweis Kiad Budapest, 2000

Rszletes tartalom
ti

Az O lv a s h o z ............................................................................................................................................................13
Sznvegyletek kmija: szerves kmia ............................................................................................................. 15
Szn-szn k t s ............................................................................................................................................... 16
A szn mdosulatai ................................................................................................................................16
Szn-heteroatom kts ...................................................................................................................................17
A szerves vegyletek csoportostsa ............................................................................................................. 18
Elektroneltoldsok a szerves m olekulkban................................................................................................ 20
A szerves kmiai reakcik ttekintse ......................................................................................................... 22
S z te re o k m ia ........................................................................................................................................................... 25
Kirlis m o le k u l k ............................................................................................................................................26
Az enantiomerek trszerkezete .............................................................................................................27
Az enantiomerek tu lajd o n sg ai.............................................................................................................28
Az optikai aktivits .........................................................................................................................................28
A relatv s az abszolt k o n fig u rc i .............................................................................................................30
A D/L rendszer: relatv k o n fig u r c i ................................................................................................... 31
Az R/S rendszer: a konfigurci ltalnos je l l s e ..............................................................................32
Molekulk tbb kiralitscentrummal .............................................................................................................33
Molekulris d iszim m etria............................................................................................................................... 35
Kirlis vegyletek szintzise ......................................................................................................................... 36
Racm elegyek elvlasztsa............................................................................................................................ 37
Sznhidrognek ..................................................................................................................................................... 39
Teltett sznhidrognek: alknok (paraffinok) ............................................................................................. 39
Az alknok konformcija ................................................................................................................... 40
Az alknok szerkezeti iz o m ri ja ......................................................................................................... 42
Az alknok elnevezse ......................................................................................................................... 42
Alkilcsoportok elnevezse ...................................................................................................................45
Az alknok fizikai tulajdonsgai ......................................................................................................... 46
Kolaj s szrm azkai............................................................................................................................ 46
Teltett gyrs sznhidrognek: cikloalknok ............................................................................................. 47
A ciklohexn szk- s kdkonform cija............................................................................................. 48
Szubsztitult ciklohexnszrmazkok: axilis s ekvatorilis k t sirn y o k .....................................48
Diszubsztitult szrmazkok: cisz-transz (geometriai) iz o m ria........................................................50
Tbbgyrs teltett sznhidrognek.......................................................................................................51
Teltett sznhidrognek kmiai reakcii .......................................................................................................52
Az alknok gse (oxidcija) .............................................................................................................52
Az alknok halognezse ...................................................................................................................... 52
A halognezs mechanizmusa: gyks szubsztitci...........................................................................53
Teltetlen sznhidrognek: alknek s alkinek ........................................................... ;
54
Az alknek szerk ezete............................................................................................................................ 54
Az alknek cisz-transz (geometriai) izomrija .................................................................................56
Butadin: a ketts ktsek delokalizcija .......................................................................................... 56

8 Rszletes tartalom
Konjuglt ketts kts vegyletek stabilitsa s fnyabszorpcijuk................................................ 58
Szn-szn ketts kts r e a k c i i........................................................................................................... 59
Izoprnvzas vegyletek: terpnek, k aro tin o id o k ............................................................................... 63
A lk in e k .................................................................................................................................................... 72
Az acetiln elektronszerkezete...............................................................................................................73
Aroms v e g y le te k ...........................................................
75
A benzolmolekula szerkezete ........................................................................................................................75
A benzol szerkezete Kekul a la p j n ..................................................................................................... 76
A benzolmolekula elektronszerkezete.................................................................................................. 76
Az aroms vegyletek stabilitsa ..................................................................................................................78
Az aroms sznhidrognek izomrija ........................................................................................................ 80
Az aroms sznhidrognekbl levezethet c so p o rto k ......................................................................... 81
Az aroms sznhidrognek ttekintse ........................................................................................................ 82
A benzol s homolgjai
. . . 82
Kondenzlt gyrs aroms sznhidrognek.........................................................................................83
Aroms heterociklusos vegyletek ...............................................................................................................84
ttag heterociklusos vegyletek aroms j e l l e g e ............................................................................... 85
Hattag heterociklusos vegyletek aroms jellege ..............................................................
86
Aroms vegyletek kmiai re a k c i i...............................................................................................................87
Elektrofil szubsztitci........................................................................................................................... 88
Szubsztituensek irnyt hatsa ........................................................................................................... 91
Tbbgyrs aroms sznhidrognek s aroms heterociklusok reakcikpessge.......................... 93
H alogntartam szerves v eg y le te k .....................................................................................................................95
Halognvegyletek ellltsa s kmiai r e a k c i ik ......................................................................................95
Nukleofil szubsztitci..............................................
96
Elimincis re a k c i k .............................................................................................................................. 97
Fontosabb halognszrm azkok.....................................................................................................................98
Alkoholok, fenolok ............................................................................................................................................... 101
Alkoholok s fenolok csoportostsa ..........................................................................................................101
Alkoholok s fenolok fizikai tulajdonsgai ................................................................................................ 103
Hidrognktsek kialakulsa .......................................................................................................... 104
Alkoholok s fenolok el lltsa...................................................................................................................105
Alkoholok s fenolok kmiai tu lajd o n sg ai................................................................................................ 106
Sav-bzis jelleg ...................................................................................................................................106
terkpzds......................................................................................................................................... 108
D ehidratlds......................................................................................................................................108
szterkpzds......................................................................................................................................108
Oxidci ............................................................................................................................................... 109
Alkoholok s fenolok jellemz kp v isel i................................................................................................... 110
Alkoholok s fenolok szrmazkai ................................................................................................... 112
terek ..................................................................................................................................................................... 113
terek e l llt sa ............................................................................................................................................ 114
terek tu lajd o n sg ai......................................................................................................................................114
Fontosabb t e r e k ............................................................................................................................................ 115
Szerves vegyletek ............................................................................................................................................... 117
Tiolok (merkaptnok) ...................................................................................................................................118
T io te re k .........................................................................................................................................................119
Oxo vegyletek ..................................................................................................................................................... 121
Aldehidek s ketonok elnevezse ................................................................................................................121
Oxovegyletek fizikai tulajdonsgai.............................................................................................................122
Oxovegyletek e l llt s a .............................................................................................................................123

Rszletes tartalom 9
A karbonilcsoport kmiai reakcii .......................................................................................................... 124
Nukleofil addcis re a k c i k ................................................................................................................. 124
Kondenzcis reakcik ....................................................................................................................... 126
Oxidcis s redukcis talakulsok ................................................................................................. 127
Oxo-enol tautom ria...........................................
127
A ldoladdci.......................................................................................................................................... 129
Fontosabb aldehidek s ketonok ................................................................................................................. 131
K in o n o k ......................................................................................................................................................... 133
Kinoidlis szerkezetek a biokmiban . . ..................................................................................... 134
Nitrogntartalm szerves v eg y letek ................................................................................................................. 137
Aminok ..........................................................................................................................................................137
Az aminok fizikai tulajdonsgai ...........................................
139
Aminok ellltsa.......................................................................................................................................... 140
Az aminok kmiai tulajdonsgai ................................................................................................................. 140
Az aminok bzikus j ellege ................................................................................................................. 141
Az aminok nukleofil r e a k c i i.............................................................................................................. 143
Az aminok biolgiai jelentsge ................................................................................................................. 145
Alifs aminok ...........................................
145
Neurotranszmitter a m in o k .................................................................................................................... 146
Pirimidin- s purinbzisok ................................................................................................................. 148
A nitrogntartalm heterociklusos vegyletek biolgiailag fontos szrm azkai...................................... 149
ttag heterociklusos v eg y letek ........................................................................................................149
Hattag heterociklusos vegyletek .....................................................................................................152
Kondenzlt heterociklusos vegyletek .............................................................................................. 154
Sznezkek...................................................................................................................................................... 156
Szulfonamidok: a kemoterpia k e z d e te ........................................................................................................158
A lkaloidok...................................................................................................................................................... 159
K arbon savak..........................................................................................................................................................163
Karbonsavak elnevezse ..............................................................................................................................163
Karbonsavak fizikai tulajdonsgai .......................................................................................................... 166
Karbonsavak e l llt sa .................................................................................................................................168
Karbonsavak kmiai tulajdonsgai .............................................................................................................. 168
Savi e r s s g .......................................................................................................................................... 169
S k p zs................................................................................................................................................ 170
D ekarboxilezds.................................................................................................................................171
Oxidci az l szerv eze tb en .............................................................................................................. 171
Fontosabb mono- s dikarbonsavak.............................................................................................................. 172
Z srsavak................................................................................................................................................ 175
D ete rg e n se k .......................................................................................................................................... 177
Prosztaglandinok .................................................................................................................................179
A termszetben elfordul hidroxikarbonsavak ........................................................................................ 180
181
Fontosabb hidroxikarbonsavak ........................................................
Oxokarbonsavak (ketokarbonsavak) ...........................................................................................................183
Ketontestek ................................................................................................................
185
A trikarbonsav-ciklus....................................................................................................................................185
A trikarbonsav-ciklus rszfolyam atai..................................................................................................187
Karbonsavak szrmazkai .................................................................................................................................189
Karbonsavszterek ....................................................................................................................................... 189
szterek ellltsa ..............................................................................................................................190
szterek hidrolzise: elszap p an o sts..................................................................................................191
Egyszer s z te r e k .................................................................................................................................191
Tioszterek ....................................................................................................................................................194
S avanhidridek............................
195
Savhalogenidek ............................................................................................................................................. 196

10 Rszletes tartalom
S a v a m id o k ......................................................................................................................................................196
Sznsavszrmazkok...................................................................................................................................... 197
A m in o s a v a k ............................................................................................................................................................201
Az aminosavak szerk eze te............................................................................................................................ 201
A fehrjket felpt aminosavak csoportostsa ............................................................................. 201
Termszetben elfordul ritka a m in o sa v a k .......................................................................................204
Az aminosavak optikai sajtsgai ................................................................................................................205
Az aminosavak sav-bzis jellege ................................................................................................................206
Az aminosavak kmiai reakcii ...................................................................................................................210
Az aminocsoport reakcii ...................................................................................................................210
A karboxilcsoport re a k c i i...................................................................................................................214
Aminosavelegy ek analzise ......................................................................................................................... 214
Aminosavak elek tro fo rzise................................................................................................................214
Ioncserl krom atogrfia......................................................................................................................215
Nagy felolds foly adkkrom atogrfia................................................................................................ 216
Peptidek s fehrjk ............................................................................................................................................217
A peptidkts trszerkezete ......................................................................................................................... 218
Peptidek s fehrjk aminosavszekvencijnak meghatrozsa ..............................................................220
Amino- s karboxi-terminlis aminosavak azo n o stsa....................................................................220
A polipeptidlnc rszleges hidrolzise: frag m en tci ja....................................................................221
Edman-fle le b o n t s ............................................................................................................................ 221
Aminosavsorrend megllaptsa tfed peptidek segtsgvel ....................................................... 222
Peptidek s z in t z ise .........................................................................................................................................223
Termszetben elfordul p ep tid e k ................................................................................................................224
A fehrjk ltalnos jellemzse ...................................................................................................................228
A fehrjk csoportostsa ...................................................................................................................229
A fehrjk fizikai s kmiai tulajdonsgai..........................................................................................230
Fehrjk tiszttsa ............................................................................................................................... 232
Fehrjk t rsz e rk e z e te .................................................................................................................................. 233
Msodlagos szerkezet ..............................................
234
Harmadlagos szerk ezet.................................................................................................................................. 237
A fehrjeszerkezet tpusai ...................................................................................................................239
Negyedleges sz e rk e z e t......................................................................................................................... 242
Sznhidrtok ........................................................................................................................................................ 243
Monoszacharidok .........................................................................................................................................243
A monoszacharidok sztereoizomrija .............................................................................................244
A monoszacharidok gyrs szerkezete .............................................................................................248
A monoszacharidok kmiai sajtsgai, cukorszrm azkok........................................................... 251
A monoszacharidok jelentsebb k p v is e l i.......................................................................................254
A monoszacharidok szrmazkai ...................................................................................................... 256
A glikolzis: a cukor-foszftok szerepe az intermedier anyagcserben ........................................... 258
Diszacharidok ............................................................................................................................................... 261
Nem redukl diszacharidok................................................................................................................261
Redukl diszacharidok ......................................................................................................................263
O ligoszacharidok..................
265
Oligoszacharidok a fehrjkben: glikoproteinek ............................................................................. 265
Poliszacharidok ............................................................................................................................................266
T artalktp an y ag o k ............................................................................................................................ 267
V zsznhidrtok.................................................................................................................................. 270
Mukopoliszacharidok ......................................................................................................................... 272
A baktriumok s e jtf a la ......................................................................................................................... 274

Rszletes tartalom 11
Lipidek ...................................................................................................................................................................275
Foszfogliceridek.............................................................................................................................................276
S zfingolipidek................................................................................................................................................280
S zte ro id o k ...................................................................................................................................................... 283
K oleszterol.............................................................................................................................................284
Szteroidok vltoz funkcival ....................................................................................................................286
D -vitam in o k ..........................................................................................................................................286
E p esav ak ................................................................................................................................................288
Szteroidhorm onok................................................................................................................................ 289
Szteroidglikozidok................................................................................................................................ 292
A biolgiai membrnok szerkezete s tu lajd o n sg ai..................................................................................292
Lipid kettsrteg....................................................................................................................................293
Folyadk-mozaik membrn: fehrjk a lipid kettsrtegben............................................................294
A lipid kettsrteg aszimmetrikus sszettele ..................................................................................295
Nukleotidok, nukleinsavak ................................................................................................................................ 297
N u k leo tid o k ................................................................................................................................................... 297
Pirimidin- s purinbzisok .................................................................................................................297
N ukleozidok..........................................................................................................................................299
N u k leo tid o k ..........................................................................................................................................300
Nukleotid koenzimek .......................................................................................................................... 303
Polinukleotidok .............................................................................................................................................306
A dezoxiribonukleinsav (DNS) kmiai s z e rk e z e te ........................................................................... 306
A DNS ketts hlix ...................................................................................................................... . 308
A DNS szerkezetvltozsai.................................................................................................................309
A cirkulris DNS s DNS-fehrje komplexek ..................................................................................311
A DNS bzissorrendj nek meghatrozsa ........................................................................................ 312
A ribonukleinsav (RNS) kmiai szerk ezete........................................................................................ 316
Az RNS msodlagos s harmadlagos sz e rk e z e te .............................................................................. 316
Az RNS biolgiai s z e re p e .................................................................................................................... 316
T r g y m u ta t ......................................................................................................................................................... 319