ACH KHOA HA NOI IG NGHE HOA HOC INGHE HUU CO - HOA DAU }. TSKH, PHAN DINH CHAU. eC TT er SY RA Mt HUU CO}TRUONG DAI HOC BACH KHOA HA NOI KHOA CONG NGHE HOA HOC BO MON CONG NGHE HUU CO —- HOA D PGS. TSKH. PHAN DINH CHAU CAC QUA TRINH CO BAN TONG HOP HUU CO Cn lan thit hai cé sia chita va b6 sung) eS NHA XUAT BAN KHOA HOC VA K¥ THUAT HA NOILOI NOI DAU Cong nghé tng hap cdc hgp chat hitu co ndi chung va cde hgp chat cb hoat tinh sink hoc néi riéng (duge phdm, m§ phdm, cdc thude bdo vé thie vat...) rat cdn thiét t6i nhiing hiéu biét sau vé hod hoc, dac biét la hod hoc hitu ca, vé cdc phuong phdp chuyén hod thong thuéng trong tong hop cdc hop chat hitu co, vé cde phuong phdp néi dai mach cacbon, vé cdc phutong php téng hop ldp thé, vé cdc phuong phdp phan ldp, tinh ché, lam sach cée hop chdt hitu ca. Céc kién thite chung ca ban vé hod hoc hitu co da duge trang bi trong mon hoc “Hod hoc hitu co co bdn” nhung trong nhiéu trudng hop nhing kién thite 46 vdn chua dii ddp img cho nhu edu diéu ché’ cde hop chat lam thudc 6 cdiu trite phite tap ma trong quy trinh téng hgp dé Iqi cé nhiéu giai doan, gdm cé hang chuc bude néi tiép nhau, diéu kién téng hop phicc tap - cing mot bic trong mét phén tit hitu co cé chita nhiéu nhém chitc cé thé cting tham gia phan itng. Nhiing hic nhut thé nay cdn phdi lua chon duge diéu kign phén ting phi hgp, xtic téc va cdc tée nhdn dic higu. Dé dép ting cho nhiing doi hoi nay, tit nhiing nam dau cia thap kj} ba muoi thuge thé ky XX Groggins dd dua ra mét mén hoc mdi goi la “Céc qua trinh co ban tdng hgp hitu co”, nd hao ham céc qué trinh co ban khdée nhau, trong méi qué trink dé téng két lai nhiing méi lién quan khée nhau sit dung dé diéu ché ra nhitng hop chat trung gian va thank phdm khdc nhau trén quy mo cong nghiép. Trong méi qué wink 45 dé cp dén toan b¢ cae phan ting hod hoc, cde vi du quen thuge da duge trién khai trén quy m6 sdn xudt cong nghiép ma da dugc thyc té kiém ching mét cdch khoa hoc. Cac qua trinh co ban nay da duac img dung trong vige téng hgp ra cdc hgp chdt trung gian ciing nhut sdn phdm cuéi cing cia ngdnh cong nghiép san xudt duge phdm va phim nhugm ut nhing ngudn nguyén ligu khéc nhau, Theo céc tde gid thi céc qué trinh co ban néu trén trong linh vue cdc hop chat hitw co duge chia than hai nhém: Nhém thit nhdt la ede qué trinh co ban thong dung (nhiéu ngank, nhiéu linh vuc sit dung dén) va nhém thit hai 1a cde qud trink co ban dac bigt (it nganh, it linh vue sit dung dén, ddc thi cho mét s6'it nganh sit dung). Nhém thit nhdt gdm cdc qud trinh wong déi thong dung, nhiéu tink vuc cong nghiép hod chat sit dung dén nhut cdc qué trinh hink thank nhém thé va bién adi nhém thé. Voi cdc qué trinh nay cé thé dua vao cdc hop chat hitu co nhiing nhém chite (nitro, sunfo, halogeno, axyl, ankyl, amino, diazoni, azo, este, hydroxy, oxo v.v...) va day cling la ngi dung ctia mon hoc “Céc qud trinh co ban téng hap hitu co” nay.Nhém thit hai la nhém dugc goi la cde qué trinh co ban dac bigt. Ligt ké vao nhém nay gdm cdc phuong phdp tong hop dac biét - cde qud trinh co ban nay chi duoc st dung trong mét sé nganh cong nghiép hod chdt nhat dinh ma thoi, dac biét la nganh cong ughé sdn xudt hod duge nhu cde qua trink noi dai mach cachon, céc phuong phép 1éng hop lap thé dac hiéu. Cac qué trinh co bin ddc bigt nay sé duge trink bay trong cudn “Céc qué trinh co ban téng hop Hod duge”. Trong mén hoc “Céc qué trinh co ban téng hop hitu co” nay noi dung bao gdm 13 chong chia thanh hai phan chinh, phdn déu la cdc qué trinh co ban vé hink thank nhém thé méi (nhut nitro hod, sunfo hod, halogen hod), phén thit hai la cdc qué trinh co ban vé bién ddi nhém thé (nhw ankyl hod, axyl hod, este hod, diazo hod, oxy hod, khit hod, thus phan, hydrat hod va dehydrat hod). Voi muc dich nhdm dé hé thong hod lai nhitng van dé hod hoc co ban lien quan thidng hay bat gdp ma cdc qué trink hod hoc dé cap, nén trong méi chuong cluing 161 cé dé cap dén cde phdn nhw dink nghia phan itng, co ché phn img, cdc loai tée nkdn, cde xtc téc, phdn img phu, sdn phim phu, dung méi sit dung, cdc yéu 16 dnh hung, pham vi sit dung cia ede phdn ting va cudi cing la mét 86’ vi du cong nghé sdn xudt. Stich duoc bién scan véi muc dich lam giéo trinh hoc tap cho sinh vien nam thit thude chuyén nganh Céng nghé hod duoc - hod chdt bdo ve thie vat thugc Khoa Cong nghé Hod hoc, Trudng Dai hoc Bach khoa Ha Néi dé bé sung nhiing kien thitc can thié, cho viée bude vao hoc mon “Hod dugc va k§ thuat tong hgp”, dng théi cé thé lam ta. liéu tham khdo cho céc ban doc lam cong téc nghién citu trong linh vue tong hgp hitu co. Vi sdch méi bién soan ldn ddu nén chéc chdn con nhiéu thiéu s6t. Tac gid xir chan thanh cdm on moi sit gop ¥ cia ban doc ed vé ngi dung ldn hinh thitc dé lan 14 ban sau duge hoan thin hon. Tée gidMUC LUC LOI NOI DAU Chuong I MOT SO KHAI NIEM CO BAN THUONG GAP TRONG HOA HOC VA TRONG KY THUAT TONG HOP HOA HOC . Nguyen ly co ban thuyét dign tit Céc loai lign két hod hoc . Higu ting hod hoc 1.4, Mot s6 quy téc thé trong nhan benzen, anh huéng ciia higu ing I va E 1.5. So luge vé phan logi va co ché cia céc loai phan ting Chuong 2 NITRO HOA - Dai cuong . Co ché phan tng Céc san phdm phy 2.4. MOt 86 tac nhan nitro hoa 2.5. Xiic téc 2.6. Dung moi 2.7. Céc yéu t6 anh huéng dén phan ting 2.8. Pham vi sit dung cia phan ting va cita loai hop chit chtfa nitro 2.9. Céch tién hanh phan ting va phan lap 2.10. Nitrozo hod 2.11. Mot sé vi du cu thé vé sin xuat thude 2.12. Vi du vé cong nghé sén xuat nitrobenzen 30 30 30 32 33 36 36 38 38 39 39Chuong 3 SUNFO HOA 3.1. Dai cuong, 3.2. Co ché phan img sunfo hod 3.3. C4c san phdm phy 3.4, CAc tc nhan sunfo hod 3.5. Téc dung ciia xiic tc va cdc chat phy gia 3.6. Dung moi 3.7. Digu kien ciia qué trinh sunfo hod 3.8, Pham vi sit dung cia phan tig va ting dung cia cc hop chit sunfonic 3.9. Cich tién hanh phan ting (chung) 3.10. Tach va phan lap cdc axit sunfonic 3.11. Mot s6 vi dy cu thé Chuong 4 HALOGEN HOA 4.1. Dai cuong 4.2. Céc phuong phap dé tao ra cdc hgp chit halogen hifu co va co ché phan ting cia nd 4.3. San phdm phy 4.4, Tée nhan halogen hod va pham vi ting dung cua né 4.5. Xile tae 4.6. Dung moi 4.7. Céch tién han 4.8, Mot sO vi du vé digu ché thud 4.9. Mot s6 cong nghé 45 45 4s 47 47 50 51 51 52 56 56 37 64 64 64 66 66, 69 70 70 70 71Chuong 5 ANKYL HOA 5.1. Dai cuong 5.2. Céc téc nhan ankyl hod 5.3. Céc logi ankyl hod, pham vi sit dung cia né 5.4. Cac yéu t0 anh huéng én qué trinh ankyl hoa 5.5. Cach tién hanh 5.6. Vat ligu ché tao thiét bi 5.7. Mot s6 vi du digu ché thude 5.8. Mot s6 cong nghé Chuong 6 AXYL HOA 6.1. Dai cuong 6.2. Céc te nhan axyl bod 6.3. Co ché phan ting 6.4. San phim phy 6.5. Xiic téc 6.6. Dung moi 6.7. Céc yéu t6 anh hurdng t6i qué trinh axyl hoa 6.8. Pham vi sir dung cita phan ting 6.9. Mot s6 vi du digu ché thude 6.10. KF thuat an toan axyl hod 6.11. Mot s6 vi du cong nghé san xuat Chuong 7 ESTE HOA 7.1. Dai cuong 7.2. Co ch€ phan ting 86 86 87 88 ol o1 91 98 98 99 101 101 102 102 102 102 103 104 104 109 109 tT7.3. Xiie téc cita este hod 7.4, Dung méi cia phan ing 7.5. Cée yéu 16 anh huéng dén qué trinh este héa 7.6. Pham vi sit dung 7.7. Cach tin hnh phan ting 7.8. Mot s6 vi du cu thé vé diéu ché céc chat thuéc 7.9. Mt s6 vi du cong nghé Chuong 8 OXY HOA 8.1, Dai cuong 8.2. Thuyét oxy héa. Co ché phin ting oxy hoa 8.3. Cac phan tng phy, san phim phu 8.4, Céc téc nhan oxy hod 8.5. Pham vi sit dung cia phan ting 8.6. Thiét bi 8.7. Ky thugt an toan 8.8. Mot vai vi du Chuong 9 KHU HOA 9.1. Dai cuong 9.2. Tée nhan khir hod 9.3. Cée phin ting phy, sin phdm phy 9.4. Pham vi sit dung 9.5. Hydro phan 9.6. Mot s6 vi dy 3 4 4 118 119 ng 120 126 126 128 132 132 137 147 148 148 154 154 154 168 168 179 18110.1. 10.2. 10.3. 10.4. 10.5. 10.6. 10.7. 10.8. IL. 1.2. 11.3. 114. 12.1. 12.2. 1zA. 12.4. 12.5. 12.6. 12.7. Chuwong 10 DIAZO HOA Dai cuong Dac diém cita musi diazoni Ung dung ciia cdc hop chat diazo Co ché cia phan ting diazo hos ‘Cac yéu t6 anh huéng dén qué trinh diazo hod Nguyen tc tign hanh diazo hod Céc phan ting cia mudi diazoni ‘Thiét bj va an toan Chuong 11 DECACBOXYL HOA Dai cuong Co ché phan tng Pham vi sir dung ciia phan tng MOt so tmg dung cy thé cia phan img trong téng hgp hod duge Chuong 12 PHAN UNG THUY PHAN Dai cuong Co ché cia phan ing thuy phan Cfc t4e nhan thuy phan Pham vi sir dung Chon vat ligu Lim thiét bj cho phan ting thuy phan Kf thuat an toan lao dong Mot vai vi du 188 188 188 189 189 191 194 194 198 200 200 200 200 205 207 207 207 208 212 227 227 228Chuong 13 HYDRAT HOA VA DEHYDRAT HOA 13.1. Dai cuong, 13.2. Céc phan ting hydrat hod 13.3. Cc phan ting dehydrat hod 13.4. An toan ky thuat 13.5. Mot vai vi du TAI LIEU THAM KHAO 235 235 236 240 243 243 246Chuong 1 MOT SO KHAI NIEM CO BAN THUONG GAP TRONG HOA HOC VA TRONG KY THUAT TONG HOP HOA HOC Dé thuan tién cho viée gidi thich co ché cdc loai phan ting hod hoc va céc qu trinh hod hoc co ban, trong chuong nay ching t6i xin duoc nhiic lai mot s6 khai nier co ban thudng hay gap trong hod hoc. LL. NGUYEN LY CO BAN THUYET BIEN TU Nguyén tir g6m nhan va cde dién tit chuyén dong quanh nhan. Nhan mang die tich duong, khdi lugng chiém hau hét khéi lugng nguyén tit. Dien tir mang dién tich a1 6 kh6i Iuong khéng dang ké. Nguyen tir cé dign tich trung hoa nén dién tich cia nha bing s6 dién tit trong nguyén tit d6. Cac dién tir chuyén dong quanh nhan thinh cé dim may chia thanh nhiéu lép mot theo quy luat nhat dinh, 16p ngo’ higu 18 K, lop thit hai ky higu 1a L, lép tht ba la M_ v.v... Lép dign tir ngoai cing — “Iép dién tir hod tri” quyét dinh tinh chat ly hod he cia nguyén ur. Lép dién tir hod trj cha nguyen tir thay déi tir 1 dén 8. cing duge k Nguyen ly co ban cita thuyét dién tit; Tat ed cdc bin déi hod hoc ciia nguyen t déu do su bign ddi ciia dp ditn tit ngoai cing ciia nguyén tit. Khi lop ngoai cing da 8 dien tir (trit hydro chi c6 2) thi khong xay ra phan dng nia. Trong hod hoc goi quy ta nay Ia “quy tac bo 8”, 1.2. CAC LOAI LIEN KET HOA HOC ‘Theo nguyen ly cia thuyét dién tr, trong cc phan ting hod hoc cdc nguyén tir dé cé Khuynh huéng thu xép thé nao dé lép ngoai cing cla n6 bao hoa cé 8 dién tit va tr thanh nguyén ti én dinh bén vitng nhu khi tro. Nguyen tir c6 hai céch sip xép dién tit dé tao ra cau tric cla khi tra, Céch thir nhdt: Chuyén giao dign tit gitta nguyén tit may véi nguyén tir khéc Trong trudng hgp nay tao ra “lién két dién hod tri”. Thi du nhw trong phan tir NaCl. Na + ct“Lien két dien hod tri” nay cdn goi 1a “ign két ionic” hay lién két “di cue” Cach thit hai: 1a chung nhau mot doi dign tit, moi nguyén tir g6p ra mot dign tir vay cd hai nguyén tir déu cé 1ép ngoai cing tém dién tir tao ra nguyén tit trung hoa. ‘Trong trudng hop nay hinh thinh nén “lién két déng hod tri”, trong chuyén mén cdn goi la “lién két déng cuc” hay “lién két khong phan eye”. Vi du trong phan tit Cly + —» cI-Cl Trong “lién két déng hoa tri” cé mot trudng hop dac biet 18 doi dién tir chung khong phai do méi nguyén tir g6p vao mot dign tir ma doi dign tir chung do mot nguyén tic tham gia phan img cung cap. Vi du d6i véi phan tir NH,CI 1a ow, Trong trudng hop nay nito thita hai dign ti ur do cho H ciia HCI, N va H 6 chung mot d6i dién tir, tao nén mot lién két déng hod tri méi va NH,* duge hinh thanh, khéi NH,! nay néi v6i CI” bang lién ket ionic dé cho NH,Cl. Nhu vay trong NH,Cl vita c6 cA “lien két déng hod tri” vita c6 cA “lién két dign hod tri”, ta goi d6 1a “ign két phoi tri”. Lién két phoi tri dugc ky higu bing mdi ten di tir nguyen tir cung cap doi dign tir dén nguyén tir nhan doi dién tir: HU we (HNH] cl H 1.3. HIEU CNG HOA HOC 1.3.1. Su phan cue ca lién két déng hod tri — Hien tng 7 ‘Trong mét phan tir 6n dinh thi gitta cdc nguyén tir trong cing mot phan tir lai c6 sy anh hudng tyong hé lén nhau lam thay déi sy phan b6 dién tich trong phan tit. Néu mot phan tir gém nhting nguyén tir hogc nhém nguyen tir gidng nhau thi doi dign tir chung trung hoa c& hai nguyén tit, lic nay dam may dign tir phan b6 déu gitta hai nguyén ti hodc hai nhém nguyen tir. Vi dy trong phan tir Cl, hoae CH;-CHsy. a-a CH3- CH; Nhung néu lién két déng hod tri néi hai nguyén tr hoac hai nhom nguyén tit khac 12nhau thi doi dién tir gop chung sé léch vé mot phia, dam may dién tir st lech vé phia nguyén tir cé do am dién 1én hon. Vi dy trong phan ti HCl hoac CH,-Cl. 8) H-al Hq? hoa H-C a) cHy-a cH CPO hoge CHCl Su chuyén léch dign tir vé mot phia Lam cho hai nguyén tir c6 dign tich khée nhau, nhiing dién tich nay khéc nhau rat nhd va duge goi la dign tich rigng phén ky higu 1a &(+) va 8(-). Hign tugng chuyén Igch dign tir vé mot phia nay duge goi la “higu tng cam ting” hay higu tng / (inductive). Dink nghia: Higu tng cam ing (higu ting J) 1a su phan cue cha lién két déng hoa trj do sy chuyén léch vé phia mot trong hai nguyen tir eta doi dién tit chung tao thinh mot phan tir cé cyc véi dién tich khéc nhau rat nh6 goi 1a dign tich riéng phan. Quy dinh gid tri cia higu ng /. Néu lay su phn cc cia H gan vao lien két déng hod tri lam chudn thi nguyen tir hoac nhém nguyen tir hut dién ti manh hon H sé c6 gid tri higu tng am ky higu 18 -/, ngugc lai nguyen tir hodc nhém nguyén tir hut dién tir yéu hon H sé cé gia tri higu tng duong ky higu +/. Doi dién tit chung sé Iéch vé phia nguyén ti hit dién tir manh va 6 dé tinh am dién tang, ic nay hiéu ving 1a -/. Truong hop nguoc lai 1a +/. Trong bang tuan hoan c6 quy tac chung sau: ‘Trong cing mét chu ky (hang ngang) higu tng —/ tang cing nguyén tir sé. Trong cing mt nhém (hang doc) higu ting —/ gidm cing voi viée tang cla nguyén tir s6. Vay trong bang tuén hoan nguyén tt F c6 higu ting —/ 16n nhat. Moi lién quan cia mot s6 nguyén tr hodc nhom nguyén tit nhu sau: I cl 18841 > 163841 1.3.2. Su chuyén dich cia dign tit trong cfc lien két kép - higu ting FE Trong phan 1.3.1. ta da nghién citu higu ting / sy chuyén djch cia dién tir trén lien ket cacbon - cacbon. ‘Trong mot phan tir cé chifa lien két kép (ndi doi, néi ba) su chuyén dich dign tit xay ra theo mot céch khéc, céc dién tir khong chi chuyén dich én truc lién két ma con chuyén dich 3 ci ngoai truc nay. Trong lien két kép 6 chifa mot lién két o a mot hose hai lién két m. ‘Trong lién ket o cdc dign tir chuyén dich trén truc lién két, con céc lign két x céc dién tir chuyén dich ngoai truc lién két. Vi dy trong lign két C=O cia mét xeton, c6 hai doi dién tit chung. Mot doi tao ra n6i don bén ving — lién két o — ign két nim tren truc gitta nguyen ti C va O, con doi dign tir cdn lai tao thinh lign két m & ngoai truc ciia C va O. Nang luong lién két x chi bing 1/3 nang lugng lién két ciia o, chinh vi thé trong phan ting hoa hoc thuing lign két 1 dé bi ph vG. Trong trang thai phan ting cing véi higu tg / cdc dign tr cla lién két x chuyén dich vé phia nguyén tir O — nguyén tit mang din tir am — nguyen tir nay c6 di 8 dign wr va mang dign tich am cdn nguyen tit C chi c6 6 dign tir mang ign tich duong: ©, Pero hay PcG be Su chuyén dich dién ti nhu trén cia déi dign tir x duoc goi 1a hiéu ting E (electromere), n6é duoc k¥ hiéu bang mot mii tén cong. & c& Nhu vay higu dng E chi c6 & phan tir cha lien két kép va chi thé hign ra khi phan tir d6 tham gia phan ting hod hoc. 1.4. MOT SO QUY TAC THE TRONG NHAN BENZE! ANH HUONG CUA HIEU UNG I VA E Nhan benzen chifa nhiéu nguyen tit H & nhiing vj tri khdc nhau, khi dua nhing nguyén ti hay nh6m nguyén tir (nhém chtic) khée nhau vao thé nhitng hydro nay lic 14déu xem ra vé cling phic tap, c6 rat nhiéu cdch thé, nhung thuc t€ qua kinh nghiém cia hang thé ky lam thuc nghiém ngudi ta rdt ra nhing quy tac sau: 1. Chi thé duge hydro cia nhan benzen bing cdc nhém thé di dién tir X, cd nghia la céc quy tic sau day chi c6 gid tri v6i cc phan tg thé 4i dign tit (S_) (khong C6 gid tr] d6i voi thé di nhan, thé g6c), nhém thé the nhat X & bat ky vi tri cacbon nao trong nhan benzen déu tuong duong nhau. oor 2. Vi tri nh6m thit hai Y g4n vao nhan thom phu thudc vao ban chat nhom da cé sin trong nhan (nhém thé nhat dugc ky higu 1 X) chit khong phu thude vao tinh chat ca nhém moi (dugc ky hiu 1a Y) va chil yéu xay ra hai kiéu thé sau: - ¥ sé vao vi tri octo va para (so vi X) ho&c - ¥ sé vio vi tri meta (so véi X). x X nhom thé loai I —E—ec x Oo ¥ Y x Xahom thé loai I a | Aahooi thé tog, Y 3. N6u nh6m thé thét nhat, c6 sn trong nhan (X) 18 nh6m thé thude loai I (da s6 1a cdc nhém thé chifa lién két don) thi nd sé huéng nhém thé méi (Y) vao vi tri octo va para, va lam ting kha nang phan ting thé ai dign tir cia nhan thom. Ngugc lai, nhém thé c6 sn trong nhan (X) 1a nhém thé loai II (da s6 1A nhiing nhém thé chifa lien két kép) thi n6 sé hudng nhém thé méi (Y) vao vj tri meta va lim gidm tinh phan ting cia nhan thom. Sau day 1a bang phan loai céc nhém thé loai I va IL Cée quy tac tren duge gidi thich dya tren co sé cia higu tng J, E va nguyen ly luc ht tinh dién (dién tich trdi dau thi hit nhau va cing dau thi day nhau). 15Nh6m thé loai I Nh6m thé loai II -F, CL, Br, I -NO, - OH, OR, OAc - SO3H, SO,R - NH,, NHR, NR» - CHO, CH=COOH - R, CH,R, CHR, CR; - COOH, COOR, COOAr, CONH2, CONHR: - CH,Cl, CH2CN, - COR. CO COOH CH,COOH -CN - CcHs - CCl, = NOH, NOHR,, NOR, ‘Vi nhan thom (benzen) cé 6 x electron to thanh dém may dién tit mang dién tich 4m lg ling trén va duéi hé théng C-C cia nan thom nén chi nhimg nhém thé mang éi@n tich duong (nh6m di luc véi cdc dién tit) méi cé thé tin cOng vao cacbon cia nhan thom vi vay méi goi I phan ting “thé di dién ws", ky higu IA Sg. Trong phan ting Sg do Anh hudng cia cde higu ting 7, E cia cc nhém thé ¢6 sin trong nhan (X) — cdc nhém thé nay c6 thé hogt hod nhan hode 1am gidm kha nang phan Gng cia nhan do anh hudng dén su phan bé mat do dign tir trén timg nguyén tir cacbon 6 vi tri khde nhau (Ie di nhién noi nao c6 mat 49 dign tix 1én hon thi nh6m thé sé gin vao 6 d6). Chinh vi thé, nhém thé méi (Y) méi c6 thé tn cong vao vj tf octo, para hoac mera va tao ra sin phdm tuong ting theo ty 1é khéc nhau d6i véi timg nhém thé khdc nhau cing khdc nhau. MGi quan hé gitta cc loai nhém thé va higu img kém theo (higu cng /, £) cing nhu anh huéng cia chiing téi kh nang phdn img thé Sz (vi tf nitro héa) cia nhan (so sénh véi benzen), t6i kh nding huéng vi trong viéc tao céc loai déng phan, hinh thanh san phdm (0, p, m) dug chia thanh 5 nhém chinh trong bang tém tit sau: 16Nhom hgp chat mot |g 2 Be | 2% an thé cia benzen 2S Bs c| es So & 22 | Khanangphaning | -3 5 2) ¢ 3 thr Ox wp = = | Gosénh véinhan | 2 = 3 2 3 “a 8 tie 3 8 benzen) ea 28 x zs a° | as 1. [=n -1 CHX CCl, 2. +1 CoHsX >CsHs-H | o,p>m]| o,p 3. Hva+E | CoHsX>>CcHs-H |o.p>>m| o.p 4 I-11 < |+E1| CH;X>CHs-H | op>m| op I-il > HEI CoHsX m | op 5: -Iva -E | CHX>CGH-H | op NH; > OH > OCH; > NHAc > OCOCH, > CH, > Cl (Br, 1) > Cols > Col{CH,-COOH > -CH=CH-COOH. Déi véi nhém thé logi Il: N*(CH3), > NO, > CN > SO,H > CHO > COCH, > COOH > COOCH; > CONH; > “NH; 1.5. SO LUGC VE PHAN LOAI VA CO CHE CUA CAC LOAI PHAN UNG 1.5.1. Mét sé khai niém vé each phan loai cac sin phdm phan img Mot phan ting hod hoc xét cho cing 14 sy phan bé lai cla cdc dign tit hoa tri giita cée nguyén tif trong nhding phan tir tham gia phan dng (hinh thanh lai céc lien ket). Su sip xép lai céc dign tir d6 tin hanh theo mot nguyén tée co ban 1a “xdy ra theo céch nao ft lam thay déi nbat vi wi ban diu cia cae dién ti” - hay néi cach khée 1A cin it nang Iugng nhat cho sy hinh thanh lién két méi, d6 1 dinh dé co ban cia thuyét dien ur “Quy tée bién dang phan tr tdi thiéu” ciia Ingold Nhung viéc xét sw sp xép lai dign tir nhur thé nay rat phic tap vi doi Itic mot phan ting, khong phai chi IA mot qué trinh bign déi don gin ma 1A mot dy gém nhiéu qué trinh tiép néi nhau, ma méi qué trinh Iai tao ra mot chat trung gian va cdc chat trung gian nay chi t6n tai trong mot thdi gian rat ngan cing vi vay dé don gian hod ngudi ta thudng dai dién hoa hoae phan chia ching thanh timg nhém phan tmg dac trung. Cé nhiéu céch dé phan loai cdc phan ting dé, sau day 1a mOt s6 quan diém co ban ciia su phan loai dé: Céch phan logi thit nhdt 1A dua wen trang théi tinh. Dya uén két qua su hinh thanh cla sin phdm tao ra trong phan mg. Véi cach phan loai nay ngudi ta di dén duge céc loai phan tng sau: 18- Phan ting cOng (addition) ky higu la Ad. - Phin iing thé (substitution) ky hiéu la S. ~ Phan ting tach loai (elimination) ky higu la El. - Phan ng chuyén vj (mot qué trinh gém nhiéu phan tng). - Phin Gng oxy hod, khif hod... Céch phan logi thit hai & dya tren trang théi dong, cach phan loai nay dya vao tinh chat céia qué trinh phan ting xay ra, dua vao céch phé huy cia lign két ci, hinh thanh lién két méi, cy thé 18 dya vio su dift ra cla céc lién ket, lién két dé cat ra theo céch nio, cn phan hay di phan? RYX —= Rk +X (can phan—> tao ra géc ty do) i RO XO oe pe so Mi Phan — Yo ra cxe fom Nhu phuong trinh trén cho thy trong viée tich lién két theo c4ch can phan sé hinh thanh ra céc g6c ty do, cdn trong cach téch di phan hinh thanh ra cdc ion am, duong. Ciing vi vay ma phan tng duge chia thanh loai phan ing géc hoac phan ting ion. Céch phan logi thit ba 1a dya theo tinh chit cla cdc téc nhan, hodc cla nhém tham gia phan tng, nhém tham gia phan ting dé c6 kha nang cho hoge nhan dién tit Néu téc nhan mang nh6m nhan dién tir thi goi 14 phan ung ai dien tr (electrophy!), nguoc lai tfc nhan mang nhém cho dién tir thi phan ting dé goi 1 phan ting i nhan (nucleophyl). Ngutti ta cfing con phan loai theo bac ciia phan ting. Phan ting don phan tit, nhi phan hodc da phan (néu trong giai doan quyét dinh caa phan img chi duy nhat mot, hai hoac nhiéu phan tir tham gia vao giai doan chuyén tigp). Trong mét sé tru’ng hop con phan loai phan ting theo s6 bude cua phan tg, phan ting mot buéc, hai bude hodc nhigu bude (day chuyén). T6m lai trong héa hoc hitu co ngudi ta thudng két hop tat ca ce céch phan loai wén ca trang thdi Ginh, trang théi dong lin tinh chat cua tde nhan cling nhu bac ciia phan wing dé phan loai cdc phan tg hodc thanh nhiing nh6m dac tung. Sau day La mot s6 phan loai co ban va ky higu cita co ché cho mot s6 phan tng thudng gap: - Phin ting cong (addition) Ady, Adg, Ady - Phan Gng thé (substitution) Sy!, Sp', Sp - Phan ding tach loai (elimination) El'. Nhu vay trong céc ky higu co ch€ cia céc phan ting da néu cho biét cdc ¥ nghia sau: 19- Thit nhat: phan ting 46 thuéc loai phan ting gi, cong (Ad), thé (S), hay tach loai (El). - Thit hai: nhém tin céng (t4c nhan) trong phan ting mang tinh chat g (N), ai dién vir (E), hay 18 g6c tu do (R). - Thit ba: bac cila phan ting: bac nhat (1), bac nhi (2), hoac da phan ti (n) tham gia trong giai doan quyét dinh. ‘Vi du trong ky higu viet Sy? cé nghia 1a phan tng dé xay ra theo ca ché phan ting thé (substitution) 4i nhan (nucleophyl) nhj phan tir (2). 1.5.2. Co ché ciia mot sé loai phan img Dé minh hoa cu thé co ché chia céc loai phan ting ta lan lugt nghién ctu co ché céc Logi phan ting co ban do. 15.2.1. Co ché cde loai phan ing cong Phan ting cong 1a phan ting bao hoa lién két doi, ndi ba (goi chung 1a lién két kép) gitfa cacbon-cacbon, cacbon-oxy, cacbon-nito, cacbon-lu huynh. Trong lién két kép nang Iuong lien két gém mot lién két o va cdc lién két 7, lién két n c6 mite nang lugng cao hon lién két o va dé bi phan cuc nén trong cdc phan tng cng lien két 7 bi pha huy tao ra céc lign két o bén viing hon. Tuy tinh chat cla cdc téc nhan téin cong vao lién két kép, i dign tir, 4i nhan hay géc ma phan biét la phan img cng di dién tit (Adg), cOng di nhan (Ady) hodc cong g6c (Adp). 1.5.2.1.1. Phan ing cong di dign ut (Adg) Céc phan img bao ho’ lign két kép cacbon-cacbon thutng xay ra theo co ché cOng 4i dign tir vi ban than cdc dam may dién tit 7 ciia lin két kép 1a hoat lye cla phan diag. Vi du khi cho etylen phan ting véi khi clo ta thu duge dicloetylen. CH,=CH, + Cl, —> CI-CH;-CH,Cl Co ché phan ting trén duge minh hoa nhu sau: nhanh 20Theo cdc kiém tra dong hoc thi phan ting xay ra theo ba bude, diu tign cde dién ti % tao véi cae dign tr cita phan tir clo tao nén phtic 7 (I) (bude nhanh), sau dé phitc nay tgo thanh cacbeni ion (II) (bu6e cham), eudi cing 1a Cl!" tée dung véi cacbeni ion duong dé tao ra phan tir trung hoa IIT (bude nhanh). Nhu vay ion Cl tan cong vao dién tu x cia Lign két kép 14 bude quyét dinh cia phan dng vi thé ma phan dng nay thude loai phan ting cong ai dién tir (Ade). Cf phan ting bo hoa lién két kép C=C, C=C véi Hp, halogen, H,Q;, HX, HOX, déu thudc loai cong Ai dign tt. Xtc téc cho phan tng cOng Ai dién ur 18 céc axit Lewis (AICI, BF;...) va céc dung moi phan cuc. 1.2.1.2. Phdn ting cong di nhdn (Ady) Cac phan Ung bao hoa lien két kép gitta cacbon-oxy, cacbon-nito thudng xAy ra theo co ché cong 4i nhan. Vi du khi mot andehit hode xeton tac dung véi mét tae nhan 4i nhan (ky higu 1a H—Nu) thu duge mot san phém cong hop téng quat nhu sau: OH >eso + H-Nu —> ScK Nu Khi kiém tra déng hoc phan tmg giifa axeton va axit xianna hydric ngudi ta thay qué trinh nay xay ra: - Lién két H-CN téch ra: nhanh, 10 H-CN + OH? H,O + CN ~ Hinh thanh lién két C-Nu: I Cech oo Sf ae yk St eN - Hinh thanh lién két O-H: CN | 0° ant OH cK + Ho SOK + OH? Trong dé buéc thir nhat va thi ba 1a qué trinh nhanh con bude thit hai bude ion am CN© tin céng vao cacbon mang dién tich riéng phan duong pha vo lien két m cia cacbon-oxy, hinh thanh lién két cacbon-xiano (bude cham), ciing chinh vi vay ma phan img nay 1A phan tng cOng di nhan (Ady). Xiic tde cho cdc phan ting cOng di nhan Ia céc xiic téc bazo. 21Cic hop chat téc nhan 4i nhan bao gém céc loai sau: HCN, NaSO,H, NH,-NH3, NH,-NHR, NH,-R, NH,-OH, NH,~NH-CO-NH,, NH,-NH-CS-NH,. 1.5.2.1.3. Phan ting cOng gdc (Ad) (Radical addition) Lién két doi, ba gilfa cacbon-cacbon ciing cé kha nang cong gc. Trong nhing diéu kien nhat dinh (tac dung nhigt, xiic t4c peroxit, nang lwgng chiéu xa...) tir cée tic nhan cong hop cae géc ty do duge tao ra, cae géc nay lién két véi dién tm hinh thinh nén nhiing géc méi va géc méi tiép tuc lién két nhiing g6c ty do khéc cho ta sin phim céng hop. Vi du khi cho etylen phan tng véi HBr trong mdi trudng chtfa peroxit sin phim cOng hop duge tao ra Ia etyl bromua. Phan tmg nay xay ra theo co ché cong géc: Truéc hét duéi tic dung cia peroxit, HBr phan ly thanh géc tu do Br" va H” (budc khoi mao). Sau 46 géc Br° lién két véi din tir cila lien két 7 tao ra géc ty do cia géc cacbon va tiép tuc tao ra g6c tw do méi (day chuyén). Cudi ciing 1 bude két thtic. Cie qué trinh dé duge biéu dién nhw sau: —> H+ (Buéc khoi mao) CH}*CH, +°Brt —> (Phan tng HiBrt + "CH,-CH,-Br ——> CH,-CH,-Br + day chuyén) “CH;-CH)-Br + "Br! ——> BrCH,-CH,-Br ‘CH,-CH;-Br +H" THe CHy- Br (Buse ket thiic) H Tuong tu nhu HBr, cdc hyp chat khéc nhur halogen (Clp, Brz), céc aldehit, alcol este, polyhalogenua ankan (CHC1,, CHBr;, CCl,), hydro sunfua, tiol, bisunfat... cing c6 kha nang tham gia phan tng cong g6c trén lién két doi cia anken. Bry (Cl) = —> R-CH-CH-Br (Cl) BrCl) R’-CH,-CHO —» R-CH)-CH,-CO-CH,-R’ CCl, —> R-CHCI-CH;-CCl, CHCl, —> R-CH,-CH;-CC1, CHBr; —> R-CHBr-CH)-CHBr R-CH =CH; + Nguoc lai véi HBr, HCI va HI khong tham gia phan ting cOng g6c véi cdc anken. 221.5.2.2. Cée phin tng thé Cing giéng nhu trong phan ting cong, phan ting thé cling c6 céc loai tuong tu: thé 4i dien tit (S,), thé di nhan (Sy), thé géc (Sp). 15.2.2.1. Co ché phan ting thé i dién nt (S;) Phan ting thé 4i dign tir thudng 1A phan Ging thay thé nguyén tit hydro ciia nhan thom bang mot nhém tac nhan di dién tit, Néu nhém téc nhan di dign tir duge ky higu 18 E" thi co ché ciia phan ting thé 4i dign tir Sg duge biéu dién nhu sau: truée hét tie nhan Ai dign tr E lién két véi he dien tit x cia nhan tao ra phic -r, sau dé phic ion nay ty dinh vi chuyén sang phite chuyén ligp -o, trong qué trinh dé téc nhan di dign tir E dinh vi vao mét vi tri cacbon nhat dinh (phic -o cdn goi la benzeni ion hay phenoni ion) va cudi cing wr én dinh hod bing céch loai proton khéi phitc -o dé tao thanh phan tit trung hoa chtta nhém thé E. oO + EO = Or Gee" — ot b. or ) eyH BO Ca Cac loai phan ting ligt ké trong bing sau day déu xay ra theo cv ché phan dng thé di dién tir: + BCH & Phan ting Tén loai phan tn, ArH+HNO,—— > ArNO, + H,0 nitro héa ArH + H,SO,== Ar-SO,+H,0 sunfo héa ArH+X, —* Ar-X+HX halogen héa (X=Cl, Br) ArH +R-X == Ar-R+HCL Friedel-Crafts - ankyl héa ArH +R-cocl “Ck arcor + HCI Friedel-Crafts - acyl héa 23Phan ting ‘Tén loai phan dng AICI, CaCl ArH +CO Fe Ar-CHO Galtermann-Koch Ari + HCN + Hel “C4 Ar-CH=N*H,CI —* A-CHO Galtermann Alc, ArH +R-CN + HCl ypu ArCOR Houben-Hoesch Css CoHsy, POCl, ArH + con ArCHO + HNN cy, Vilsmeir ArH +CH,O ——> Ar-CH,OH Hydroxymetyl héa ArH + CH,O + HNR, —> Ar-CH,NR, + H. Mannich (aminometyl héa) AtH +CH,O + HCl —* Ar-CH,Cl + H,0 Clometyl héa ArH + CO, —* ArCOOH Kolbe-Schmit ArH + HNO; —> Ar-NO + H,0 nitrozo héa ArH + Ar’-N*=NCI © —> Ar-N=N-Ar’ + HCI | ndi azo 1.5.2.2.2. Phan ting thé’ di nhdn (Sy) ‘Thé 4i nhan 1a qué trinh thay thé nguyén tr hoge nhém nguyén tir X lién két v cacbon bang nhém di nhan Nu, két qua nhém X téch ra mang theo cd doi dién te: R-X +Nu —> R-Nu + X: Trong d6 tac nhan di nhan cé thé 1a cdc anion hoac chat trung hoa 6 chifa ¢ dign tit ty do: Nu= C1, BO, 1, OHM, ROO, HS, RSP, Va X thudng 1a céc nhém hut dién tu nhu —Cl, —Br, —I, -SO,H, SO,R, SO,¢ ~OH,, -OMRH, -NOR,, -N Phan img thé ai nhan dac biét cd ¥ nghia trong hod hoc céc hop chat mach thar Céc loai phan ting ghi trong bang dui day déu thudc loai phan ting thé di nhan: 24Phan tng ‘Ten loai phan ing R-OH + HX == R-X + H,0 Este héa alcol bing cdc axit vo co + R'OH= R-OR’ + H,0 Ete hod R-X + OH" —> R-OH + xO Thuy phan + ROO — ROR’ + xO Williamson + R°COO' —™ R’COOR +X Este héa + SHO — RSH + xO Mercaptan héa + OSR? —> R-SR? + XO Tiocte héa + NH,R’—> R-NHR’ HX Ankyl héa céc amin + NHR’; —> R-NR', HX Anky! héa cdc amin + NR’; —> R-N®R, XO Ankyl héa céc amin + —> R-CN + xO? Xiano héa + NO, —» R-NO, + xX Nitro héa + — RX + KO? Phan tng Finkelstein co es RAK Cope t X] Ankyl hoa B-dixeton ae + HX Friedel-Crafts ankyl héa din mg ta cé thé chia phan ting thé 4i nhan thanh hai nhom: Thé 4i nhan don phan tir ky hiéu 1a Sy' va thé 4i nhan nhi phan tir ky hieu 1 Sd Qué trinh thé 4i nhan don phan tt Sy! thudng xy ra trong hai buée theo co ché gidn tiép. Bude thi nhat nhd téc dung ciia dung moi hoac chat xtic tac nguyen tit hoac nhom nguyén tt X mang theo hai dién tt duge tach ra tir lién ket C-X vA cacbonium mang dién tich duong duge tao thanh, sau dé ion duong nay bj téc nhan di nhan Nu: tan cong tir cé hai phfa dé tao ra san phdm 18 hén hop racemic: R R 4 cham We, ei RoOnx = oc + x R° R Go «thant, Rm SR e Nui 25Co ché kigu nay thudng xAy ra khi phin Gng duge thuc hién v6i cdc anky! halogen bac ba. Can khi thuc hign phan ting thé di ti cdc ankyl halogenua bac mot hoac hai thi phan ting xay ra theo co ché tryc tiép hoc con goi IA co ché thé 41 nhan nhi phan tt $2. Trong trutmg hgp nay qué trinh pha vo lien két CX va hinh thinh lién két C-Nu cing déng thdi xdy ra va nhu vay téc nhén di nhan Nu: sé tan cong vao phia ngugc chiéu (“sau lung”) so v6i nhém rdi di (X) cia phan tit, két qua trong khodnh khac sinh ra mot phifc trung gian, sau 46 X:~ tach ra dé tao thanh lién ket C-Nu. Nut? + RO Noe te-K — > Nec + x? 7 ‘x \ Phitc trung gian gm lien ket ban phéi tri Va thanh phan cia qué trinh nay bao gid cling c6 cau trac khong gian nghich dic véi cdu tréc ban dau. Néu xudt phat 18 déng phan L thi sé cho sin phdm cia phan Ung 1a déng phin D va nguge lai. Hien tuong nay do Walden phat hin ra nén ngudi ta goi 1a “nghich dio Walden”. 1.5.2.2.3. Phan itng thé’ géc (Sp) ‘Trong cdc phan ting hod hoc mot trong nhiing san phdm trung gian dugc tao ra lt g6c ty do. Géc ty do Ta nhiing phan tir hodc nguyén tir chifa mt hose nhiéu dién tire dugc tgo thinh do qué trinh phan chia ciia céc doi dién ti wy do. Vi dy quan trong nha 1a qué trinh phd vé lién két theo cach phan chia d6i xting (can phan). A-B—> A’ + "B Va cée g6c ty do A” hoic B’ nay tiép tuc tham gia phan ting thé, thay thé ca nguyén tir hogc nhém nguyén tit c6 trong phan tir dé hinh thanh ra nhing san phan méi. Céc phan ting thé kigu nay ngudi ta goi IA phan tng thé goc (Sp). Phin tmg thé g6 thudng 1 phan img day chuyén, sin phim thu dugc nhiéu khi 14 mot hdn hop. Pha ing thé géc dugc-dic trumg bai ba qué trinh khdi mao, day chuyén, va két thie da chuyén: a) A-B > A+B (phan tng khoi mao) b) R-H + Av —> R'+ HA R'+A-B — R-A+B R-H +B’ — R' + HB R'+AB — RA+A° (cdc phan tg day chuyén) 26co) AT + AT > AA AT’+ Bo —> AB R’ +A" —» R-A cdc phan img két thtic day chuyén R'+Bo —» RB R'+R' —» RR Mu6n cho mot phan ting g6c duoc thuc hién thi diéu ki¢n ddu tien 14 phai kho mao tao ra gdc ty do. Cé thé tao ra géc ur do bang téc dung cia nhiét (nhiét héa), ban; quang (quang hoa), bing oxy hod khit, bing s6ng sigu am. Va dé két thiic phan ting da: chuyén ngudi ta cho thém vao hén hop phan ting chit ttc ché hodc chat ti goc, mu: dich 1a han ché hodc két thiic eae phan ing day chuyén. Cfc loai phan tng ligt ké sau day thudng xay ra theo co ché thé goc. - Cloro ho, bromo hod céc hgp chat hydrocacbon no mach thing & nhiét 46 ca: hoac bang quang hod. - Cloro hod mach nhénh céc hgp chat thom bang dén quang hoa. - Oxy hod c&c hydrocacbon no mach thang & nhiét do phdng bang oxy. - Sunfo-cloro hod cdc hydrocacbon mach thang mach cacbon dai bing khi clo vi sunfua dioxit (trong cong nghiép sin xuat xa phdng). - Nitro hod thé khi céc hydrocacbon no mach thdng c6 mach cacbon khong 161 bang axit nitric & nhigt do cao. 1.5.2.3. Co ché phan ting tach loai (El) Phan tng tach loai la phan ting loai khéi phan tw ban dau mot hodc nhiéu phan ti 6 phan tir lugng nhé hon va tao ra mt phan tix mdi chia mot hodc nhiéu ndi doi. Co ché phan ting cia phan ting tach loai cing gan tuong tu nhu co ché cia phar Ung thé di nhan. Ciing déu c6 phan tir R-X phan ting v6i mot téc nhan nucleophyl (Nu nao dé. Chi cé mot diém khéc nhau 14 trong phan ting thé ai nhan, nh6m di nhan Nu tar cong vio day nhém X ra khdi phan tir dé thay vao vi tri cacbon cla X trong phan tit bar dau con trong phan tng téch loai thi nhém téc nhan Ai nhan Nu ciing d4y nhém X r: khéi cacbon nhung khéng thé vio vi tri dé ma lai gianh lay mot proton & cacbon vi tr ben canh dé bio hoa cho minh két qua hinh thanh nén mot lién két doi trong phan tt méi. VA cing gidng nhu trong truéng hgp thé di nhan, phan tng téch loai ciing cé ha loai ca ché dé 1a téch loai don phan tit (El"), va téch loai nhj phan tir (EP). Sau day 12 mét s6 phan ting téch loai chinh. 2Phan dng Tén phan dng eK — >cec¢ + 1,0 dehydrat héa alcol H OH doeg —>Secd + HX dehydro-halogen héa diéu ché hydro- cacbon khong no HX x= halogen, sunfat, tozilat Seek — Seecy + R-ON dealcol héa, diéu ché hydrocacbon Vo khong no tw ete HOR o Soe OH Sco + Ne, + H,0. | Téeh los Hoffmann H NR NR Yee HSH + RSR + H,0 | THodi bien musi sunfoni bac ba H SR; SRz 1.5.2.3.1. Co ché phan ting tach logi don phan vit (El) Trong co ché phan dng téch toai don phan tt El', bude quyét dinh van téc phan ung cing giéng nhu trong phan tng Sy', cacbeni ion dugc tao ra, chat trung gian nay hodc phan ting véi Nu dé én dinh tao san phdm thé hoc cho tc nhan 4i nhan Nu néi proton & vj tri bén canh dé ty én dinh va tao ra lién két kép khong no san phim cia tach loai don phan tit (E/') duoc hinh thanh. a Lou MS H-CHC-Nu Sy!) Lo tat A io TT HOEK owe ETT +m? 1d I —™ G=¢ + NuvH (El) Nhu vay trong phin Gng ben canh san phém ctia phan ting tach loai cdn luén ludn cé sn phim cua phan tng thé, ty 1é tao thanh cia hai loai san phdm nay khong phu thugc vao nhém thé X (chi c6 vai trd trong viée tao ra cacbeni ion) ma chi phy thude vao téc nhan Nu va dung moi sit dung trong phan tng. 1.5.2.3.2. Co ché phan ing tach loai nhi phan (EP) ‘Trong phan ting tach loai nhi phan tir thi duéi tac dung ciia téc nhan di nhan Nu, viee ddy nhém X ra khdi lién két C-X va cAt loai proton ra khéi cacbon vj tri bén canh 28cling déng thoi xay ra thong qua viéc hinh thanh ra mot phifc chat chuyén tigp, sau d6, 4é én dinh hod phan tir Nu-H duge tgo ra va sin phim chia lien két doi - sin phdm cha phan ting téch loai nhi phan (£7?) duge hinh thanh. [> Nu=C=X —» Nu-C + X? 7 “IN ox. (Sy) 1 oe -X —» NuH + =e +X: (BP) Cac te nhan di nhan thuémg hay ding dé tach proton trong phan ting tach | phan E? 1a cdc bazo sau: R3N, CsH;0, HOO, ROM, H,NO, ahi Cae nh6m thé ¢é chiéu hudng t6t cho phan dng téch loai EP 1& -N™R,, PR, -SOR,. Trong phan tng EP ty 1é sin phdm cia phan ting thé va sin phdm cita phan tng ich loai Khong chi phy thuge vao cdu tric cia phan tir chia nhém thé X ma cdn phu thuge cA téc dung kh6ng gian cia né Lan dé bazo cita t4c nhan di nhan Nu. 29Chuang 2 NITRO HOA 2.1, DAL CUONG Nitro hod la qua trinh hoa hoc thay thé m@t hdc nhiéu nguyén tit hydro cia hop chat hit co bang mot hoac nhiéu nhém nitro (NO.) cla axit nitric hoae te nhan tuong duong cua nitro. R-H + HNO,—* R-NO, + 11,0 ‘Trong chuong nay chi dé cap ti nhimg hop chat tao thanh lién két C-NO, mi théi, con nhiing hgp chat co lign két nitrat (O-NO;) thi thuge phan ting nitrat hod (este hoa) sé khong dé cap trong chuomg niy. 2.2. CO CHE PHAN UNG Qué trinh nitro hod céc hop chat hitu co xay ra theo hai ban chat ciia chat duge nitro hod. igu co ché tuy thuge vio Nitro hoa nhing hop chat nhan thom pha long 6 nhigt do khong cao vay ra theo co ché thé 4i dign tir Sp, cOn nitro hod cdc hgp chat mach thing. no thé khi & nhigt do cao thi phn tng xay ra theo co ché thé géc tudo Sx 2.2.1. Co ché nitro hod cdc hgp chat nhan thom pha long Khi nitro hoa céc hop chat nhan thom trong thé léng 1 nitro hod 1A hén hop axit nitric va axit sunfuric. Khi h sunfuric thi hén hgp sunfonitric (HOSO,-ONO,) duge tao ra, sau dé hop chat nay phan ly thanh nitroni ion (NO,") va bisunfat anion. Cac qua trinh bien d6i dé cé thé biéu dign bing phuong trinh phan tng sa ta hay ding tée nhan hgp axit nitric véi anit HNO, + H,S0, == 0,5: HNO, + H,S0, == Nitroni ion méi tao thinh tén cong vio hop chat nhan thom nhu la tie nhan i dign tir theo co ché thé di dign Wr Se: 30So dé mie nang luong cia qua trinh nitro héa dugc biéu dién nhu sau: | 7 an Cr, , Cro, ore Vai trd cia axit sunfurie trong phan dng nay 1a lam xtc téc: cung cp proton dé tao ra NO,* va déng thdi ngin cin khong cho HNO; phan ly thanh Ht va NO, theo cach phan ly binh thu@ng trong nude. ciing chinh vi thé trong qua trinh phan dng khi néng do HSO, gidim di thi t6c do phan ting ciing bi gidm theo, tham chi dén mot néng dg nhat dinh phan dng khong con c6 the xiy ra Thue t ngudi ta nhan thay khi nitro hod benzen 6 25°C néu néng do axit HySO, 6 duéi 80% thi téc dé phin tng dudng nh khong dang ké. nhung néu néng do axit khoing 80% + 90% thi téc do tang Len hang nghin lan (tai khosing néng do nay NO. tao ra nhiéu nhat). Néu néng do H»SO, dat 90% = 100% thi t6e dé phan tng cing gidm. Mat khiée ngudi ta cin © hop chat nhan thom c6 chia nhém thé lowi 1 thi te do phan dng nitro hod tang len so vi benzen (rir nhém halogen) con néu c6 cha nhém thé loai II te dé phan ting gidm di so véi benzen (theo quy tic thé i dign wi Strong nhan thom). a thiiy ring trong 2.2.2. Co ché phan ting thé khi tro hoa cic hgp chat hydrocacbon nu, mach thang. Voi cée hgp chat hydrocacbon no. mach thang khi nitro héa khong ding duoc 31axit HNO, dic hoac hén hop nitrosunfuric nhu khi nitro hod céc hgp chat nhan thom vi phan img oxy hoa xy ra manh liét. Cing chinh vi thé chi c6 thé ding axit HNO, loaing (35% = 40%) hoac HNO, thé khi & nhiét do cao (300 + 500°C) dé thuc hién viée nitro hoa. Lic nay phan img x: duge xtic tée Khoi mao khi cé mat chiit it Oh y ra theo co ché thé géc ty do Sg. Phan ing ni ac halogen (Cl,. Br:) Co ché phan img nitro hod cac hgp chat hydrocacbon mach thing dugc biéu dién nhu sau: HO-NO, —* HO’ + NO} buéc khai mio R-H + NO} —* R' + H-NO, RK’ + HO-NO,—> R-NO, +"OH R-H +°OH —* RK + H-OH | K+ HO-NO,—> ROH + NO, J cdc phan ting day chuyén R + NO, — > R-NO, & +°OH —* R-OH RR —* RR cc phan ting két thiic “OH + NO, —> HO-NO, | Co ché nay gidi thich tai sao khi nitro hoa, hop chat hydrocacbon much thing ta nhin dugc san phim g6m mot hén hgp cia nhiéu chat trong d6 cé cai sin phdm oxy hod. san pham lam ngan mach cacbon. Ciing phai luu ¥ rang vé nguyén tac 6 giai doan két thtc hai g6c R" cing c6 thé két hp véi nhau nhung vi kha nang nay it xay ra hon u két hop R® \6i HO* hodc O,N* nén trong phan ting khong tim thay san pham ndi dai mach cacbon (R-R). 2.3. CAC SAN PHAM PHU Vi hai loai co ché nitro hoa trén hai loai hop chat hydrocacbon khéc nhau cing khac nhau nén san phém phu tao ra tir phan tng nitro hod hai loai hgp chat nay cing khac nhau Trong viée nitro hod céc hop chat nhan thom theo co ché thé di dign tir S_ sin phim phy la sin phdm thé hai hoac ba hydro bang hai hoac ba nhém nitro, hoac 1a cic déng phan vi tri (ecto, para, meta). Can trong nitro hoa céc hop chat hydrocacbon no mach thing thi sin phd phy la cc dan xuat nitro cé mach cacbon ngén hon hoac sin pham oxy héa 1a céc alcol. ’ is2.4. MOT SO TAC NHAN NITRO HOA Tac nhan nitro hod bao g6m cae loai hgp chat cung eaip duge nitroni ion NO. cho phan ting. Sau day Ia cdc loai hgp chat 46. 2.4.1. Cac hgp chat chifa nitration 2.4.1.1, Axit nitric (HNO,) tinh khiét Dung dich nude c6 ty wong d = 1.42. ham long HNO, la 65 + 68% axit nitric boc kh6i cé ty trong 1.49 him lugng HNO, chia 95%. Phan dng nitre hod xay ra theo phuong trinh phan ting nhu sau: Ar-H + HNO, — Art 10, + HO Nitroni ion duge hinh thanh qua hai buée 2HNO, = N,O; + HO N,O, == NO,” + NOx 2HNO; == NOs + NOx + HO G nhigt do thuéng trong axit nitric chi chita khoiing 4% nitroni ion (NO.") nhung duéi tae dyng cia proton dic bigt cia axit sunfuric thi néng do NO,’ tang len rat nhieu cing chinh vi vay khi nitro hod ngudi ta hay str dung hén hop sunfonitric. 2. 1.2. Hén hop axit sunfonitric Hén hop axit ding dé nitro hod bao gém axit nitric, axit sunfuric va nude. hér hop nay c6 tén goi la sunfonitric. Hén hop nitro hod nay mgnh hon axit nitric rat nhiéu Hon nita ding hén hop axit sunfonitric dé nitro hod cé Igi hon ding axit nitr sunfuric hit nude Lim giém kha nang pha long cia HNO,. nhu vay wanh duge tic dung oxy hod cia HNO. va lai khong can thiét phai ding axit nitric v6i néng do qué dac. trénh duge su ty thanh sin pham phy 1a din xudt polynitro. Hon hop nay duoc pha vdi ty le nhu thé nao gita HNO, : H,SO, : H20 1a do tinh chat ca chat dem nitrc hod quyét dinh. Déi véi cc hop chat thom c cua phenol, phenol ete) thi chi ding dung dich axit nitric 40% Ia du dé nitro hoa khong cin dén xc téc ca axit sunfuric. Cae hop chat thom c6 kl binh (phin Ién c6 nh6m thé loai I tir din xuat halozen) thi dé nitro hod mét phan ti m (mol) hop chat thom ngudi ta ding 1.5 mol axit nitric loai dic 68% (d = 1.42 v6i 2.2 mol axit sunfuric dac 98%. cdn déi v6i cic hgp chal thom cé kha nang phar ting thap (gém da sé cdc hop chat chia nh6m thé loai I) thi ngudi ta ding tdi 2.3 mo axit nitric loai 95 + 100% (d= 1.49 + 1.50) v6i 2.6 mol axit sunfuric dac 98% Nitro hod naphtalen thi ty Ié gidta HNO, : HySO,: H;0 18 59.1 : 24.6: 16.3. vi khat nang phan ting cao (nhur cée din xuai nang pluin dng loai trungQua trinh hinh thanh NO. sunfuric xtic tae sé 1a: cung cap cho phan tng trong trudng hop cé axit HNO, + 2H.SO, == NO,’ + H.0* + 2HSO, Trong moi tring axit H=SO, thi phan dng wen héu nh chuyén vé theo chiéu ben phaii ‘Trong thyc 1é khong chi dung duoc axit sunfuric vae hén hop axit nitro hod ma mot s6 axit Lewis cling duge ding vio muc dich nay. Vidu nhu bo triflortia + BF,OH HNO, + BF, — NO Trong trudng hop nay phan dng nitro hod sé sity ra niu sau AtH + HNO, + BF; —* Ar-NO, + BF, HO 1.3. Mudi nitrat + H3SO, Khi can nitro hoa véi néng dé axit nitric cao, dung dich nuéc cla HNO; khong dap tmg. Ngudi ta cé the ding hén hop mudi nitrat va axit sunfurie 6 thé hoan toan khan nuée. NaNO;+ H,SO, —* HNO, + NaHSO, Phuong phip nay thudng hay sit dung dé digu ché din xual polynitro. 2.4.1.4. Mudi nitrat voi anhydrit cia axit hitu co Hén hop ti nitro hod mét cach nhg nhing. tao ra mot sin phim dc nhat, hén hop phan tng khong bi nhya hod. oxy hoa. nhan mudi nitrat véi anhydrit cha axit hitu co cd thé thuc hién v c Cu(NO.):,H20 +Ac:0 —> 2HNO, + Cu(OAc), Vi du: V6i téc nhan nitro héa nay. ngudi ta 66 thé ni toluen thanh din xuat mononitvo tuong dng: or CulNO;),H,O/AC,0 owe AB) cutrosntovac,o or No x cl YL aw ‘0 hod anilin clobenzen.2.4, . Ankyl nitrat Ban than ankyl nitrat khong the nitro hod duoc. nhung dudi tic dung cua anit axit Lewis thi nd io thanh mét hén hyp nitro hos rat manh, proton h R-ONO, + H»SO, == NO,’ + ROH + HSO, Etylnitrat va axit sunfuric d nhiat do phdng di c6 thé nitro hos nitro benzen thinh in-dinitrobenzen mot cach dé ding Mot digu rat Iy thei Ja etylnitvat trong dung moi ete trong méi trung kid €6 the nitre hod duge dan chat cia pyrol. indol (vi cae hyp chat loai khung nay khong the tien hanh nitro hod trong méi trudng anit — Wong edie Moi trudng axit cée loai khung nay khong 6n dinh). dha They, SB CI ire SSNS CHy x7 CH, a Na u . Nitropentoxit va axyl nitrat (N,O¢ va ACONO)) N,O, va axyl nitrat la nhing téc nhan nitro hod manh diing dé nitro hod tong moi trudng khan nude (ding cho cde chat dé phan huy trong moi trudng nude) Vidu: COC! N,ouacono, Cre" we Xo. NO, tong méi trudng axit (H»SO,. HNO, [a chét phan ly manh tao thinh NOs". NO, + H.SO, == 2NO,*' + 3HSO/° + HL" Trong dung méi hau co (CCI,) ban than NsOs cing ¢6 kha nang phan Ly thanh NO,"*! véi néng dé thaip. cing chinh vi vay khi ean nitro hod trong moi trudng khan nude ngudi ta ding loai tac nhan nay 1a kha tign Ii va em d Os Ciing tuong ty nhy gudi ta hay ding axvl nitrat dé lan wie nhan nitro ho Vi ki phan dng n6 tao ra N,Q. va anhyrit 2Ar-COONO, == NO, + (ArCO),0 Ban than acyl nitrat duge diéu che halogenua axit tie dung voi bac nitrat ay ra tong phan ting bang cach cho Ar-COC] + AgNO, —» Ar-COONO, + AgClhoac anhydrit tac dung véi HNO, béc khéi. Ac; + HNO; —* AcONO, + ACOH Phan ig nay vira ding dé phong bé nhém amin vita dé nitro hod rit tign loi. Vi du trong khi tng hgp o-nitroanilin ngudi ta cing da str dung hén hgp anhydrit axetic ya axit HNO, dé nitro hod anilin ma khéng can bio vé nhém amino truéc khi tién hanh phan ung NHCOCH, Sy NH2 Ac,O/INO, > NO; 2.4.4, Dinitro-tetroxit N,O, N,O, 1 anhydrit cia axit nitro va axit nitric. 1A hop chat khong mau, dang tinh khiét c6 do chay —9.3°C, trén nhigt dO 501 (213°C) da chtta 1% khi NO, mau nau tren ca sé tao ra phitn ng can bing N20, == 2NO3. 6 100°C thi tao ra NO, 99% Trong moi truding HSQ, dinitro-tetroxit phan ly theo phugng trinh sau: N,O, + 3H,80, == NO,’ + NO“! + H,O"! + 3HSO,' Liic nitro hod qua trinh phan Ging xay ra nhur sat Ar-H + N,O, + H3SO,—* ArNO; + ONO-SO,OH + H,0. N,O, 1a tée nhan nitro hod manh, véi tic nhan nay c6 thé nitro hod toluen, clorobenzen thanh dan xudt nitro higu suat 88 = 96% 2.5, XUC TAC Nhu trong phan 2.4 da dé cap cdc axit proton lan axit Lewis déu c6 kha nang gitip cho nhimg tée nhan nitro hod sin sinh ra NO." ion. Cac chat hay dung nat vao muc dich nay Id axit sunfuric, axit axetic, anhydrit axetic, bo-triflorua. 2.6. DUNG MOI Hau hét cc chat thom hoac hydrocacbon mach thang dua vio dé 1ién hanh phan img nitro hod déu [a chat léng nén dung moi cho phan tng hoge 1A bain than chat din nitro hod dé hoac 12 hén hgp téc nhan nitro hod. Rat hiém trudng hgp phai ding wi dung moi khée. 2.7. CAC YEU TO ANH HUONG DEN PHAN UNG Trong cdc yéu 16 anh hudng téi qué tinh nitro hod phai ké dén niet do. dung lwong khit nude vi tic dung cua khudy tron. 362.7.1, Anh hudng eda nhigt do Phan tng nitro hed la phan dng tod nhigt manh. Nhiét tod ra nay gém hai phan chinh d6 ii nis. shan tg va nhiét tod ra do su hoa loang axit sunfuric cua nude tao thanh trong phan dng. Theo tinh toan nhigt phan ng khoang 27 + 55 keal/mol (uy thuge chat dem nitro hod). Con nhiet hod loang axit sunfuric thi cng thay déi theo nong do. lic méi dau tod ra nhiet uong 1én. sau dé gidm dan luong nhigt toa ra bién déi tH 50 + 150 keal/mol. Toe do phan tng nitro hod va higu suat phan dng phy thuge rat nhieu den ohict 60. Nhigt do (Gi wu cua phan ting phu thude vao loai hop chat vit bain chat ciia chat dem nitro hea. Nhiét do nitro hoa bién déi th -10°C dén 500°C, Thudng thi nitro hoa ede hydrocacbon no mach thang duc thc hién 6 nhiat do cao 170 + 300°C (theo ca che phan tng thé géc ty do S,). con nitro hod cde hop chat nhan thom thé long duge thuc hign ¢ nhigt do thap hon, tir —10 dén 170°C. Van téc phan dng tang khi tang nhiét do phan ting. nhung nhiét cao sé sinh ra phan tng oxy hoa. tao ra nhigu tap chat. viée diéu khign nhigt do thich hop cho timg phan Gng 1a diéu rat cin thiet bi phai 6 bo phan lm néng hoac lam lanh dé chil dor Jogi trit kha nang gay qua nbiet 2.7.2. Tae dung cia khudy tron Phan tig nitro hod thudng xéi ru gitfa hai pha mot ben La pha hw co ben tigp xtc t6t duge v6i nhau phai c6 khudy won m diéu kign cing nhigt do. khuay tron cang t6t thi phan dng xay tron cing cham thi 16¢ do phan cng cing gi la ah, Trong 4 cing nhanh, khudy pha axit. Dé hai pha ni m 2.7.3. Dung Igng khir nuée ‘Trong qua trinh ph n ting nude sé duge sinh ra va thudng xuyén hoa lodng axit han ma 6 46 vi néng dé axit thap hon yéu ciu nén phan ting khong thé nio xay ra duge mifa. Méi chat khac nhau gid wi gidi han dé cing khéc nhatl. Vi vay cén phai tinh todn sao cho dé khi phan ting két thie néng d@ axit H»SO, vin dU 1én (ren gidi han cho phép). Day 18 khi dung lugng khi nuéc, Ngudi ta tinh dung luong Kkhif nude bang cdch lap ty sé gitta axit sunfurie ban déu ding pha hén bop axit sunfonitric dua vao phan tng trén tong sO nude bun dau ding pha hén hgp axit va long nue do phan tng sinh ra. Vay dung Luong khir nuée (D.L.K.N) duge tinh theo céng thtte sau: (ci HNO, Lin H3S0,). vie hod loang ndy sé dat di mor 1 % WSO, dua vio phin tng %H,O ban diu + %H,0 do phan dng sinh ra Méi hydrocacbon nhan thom c6 mot gid wi D.L.K.N khide nhau. nghia 1a dai hoi mot néng do H,SO, khée nhau dé thyc hign dén phan dng két thuic. Chat cing kh6 nitro D.L.K.N = 37hod thi gid tri D.L.K.N cing lén. Vi du gid tri D.L.K.N ctia nitrobenzen la 7.4: clobenzen 1a 4.4: benzen 14 3.3: totulen 1a 2.4: naphtalen la 2. v.v... khi dua mot nhém NO; vio hop chat nay bang phan ting nitro hod 2.8. PHAM VI SU DUNG CUA PHAN UNG VA CUA LOAI HOP CHAT CHUA NITRO Phan tng nitro hod c6 thé thyc hi¢n duge wén ca céc hop chat hydrocacbon mach thang (theo co ché thé géc Sq) Lin cde hop chat thom (theo co ché thé di dign tu Se) dé cho din xuiit mono- hoae di-polynitrro. Céc nitroparaphin déng dang thap déu 12 nhiing chat long ding dé lam dung moi hoae dé khir thanh amin. Cie dan xuat nitro thom mot phan ding lim dung moi (nitro-benzen, nitro- tolulen), phn khéc dé khir thanh céc amin tweng ting, lam nguyén ligu cho nhiéu nginh cong nghiép trong dé ¢6 céng nghiép hod duge, phim nhudm. Nhiéu phan wr thue cé chia nhém nitro (cloramphenicol. furaxillin, niclosamit}: cde hgp chat polynitro duge ding lim thude né (trinitrotoluen TNT. winitrobenzol TNB. axit picrinic, nitroxenluloza v.v...). Mgt s6 khde duge str dyng nflu'nhing thude thir hitu co (axit picrinic; 2.4 dinitrophenylhydrazin: axit 3.5- dinitrobenzoic: 1.3.9-trinitrobenzen). 2.9. CACH TIEN HANH PHAN UNG VA PHAN LAP Déi v6i cde hgp chat thom vige nitro hed duoc thuc hién theo nguyén téc chung sau day: ‘Trong thiét bi cé lip may khudy. binh nhé giot. ahiét ké, hé théng Lim lanh. nung néng. cho vao dé chat can nitro hod lam lanh xudng dudi 10°C vita lam lanh vita Khuda’ vita nhé giot hén hop tée nhan axit nitro hod vao véi ty 1é di ghi wong myc 2.4.1.2. vé 1c dé sao cho nhiét dé phin ting khong vugt qua 10°C. Sau dé néu la céc_hop chat ei kha nang phan ting cao thi khudy them 30 phut 6 nhiet do phdng, con déi véi ciic chat kha nang phan tng wung binh thi khudy them 2 + 3 gid. ciic chit kha nang phan tng kém thi 3 + 5 gid tham chf doi Ide can thiét thi lam néng lén dé cho phiin Ging két thie. Sau khi phan dng két thuic than trong dé hon hgp phan ting vao nuée dé vun khudly k¥. sau dé néu nhu san pham [a chat ran thi loc. ra lai v6i nue, sau d6 ket tinh, Néw sin phdm 14 thé long thi chiét hén hop phan ting di dé vao nusc'dé vun v6i ete bh cloroform, ria dich chiét v6i nuée sau dé [a voi dung dich NaHCO; dén pH trung tinh, Lan khan. loai dung moi va cat lay sin phéim 6 dp suat va nhigt do thich hop. D6i Véi cde hop chat mach thing thi vige nitro hod thudng tien hanb 6 nhiet dé cao 6 thé hoi trong thiét bj lién tuc thi stin phim hén hop phn tng duge ngung tu. phan 38Iép va ria lai 6p sén phim bang nude seu dé trung hod bang dung dich natr bicacbonat, lam khan va cudi cing 1a cat phan doan 2.10. NITROZO HOA Tuong tw nhu nitro hoa, nitrozo hod 1a qua trinh dua nhém NO vao thay thé hydre trong mét hop chat hitu co. N6é duge thuc hién bang phan tng gidta hop chat thom cc chia nhém thé hoat hod nhan manh thude nhém thé loai I (nhém OH. NR3...) véi axi nitro. Axit nitro dugc to ra ngay tong phan img tir natri nitrit va axit sunfuric va trong méi trung axit nay tc nhan thé di dién ti NO* duge hinh thanh, tic nhan ndy phat (mg vi nhan thom. Qué trinh phan tng d6 viet tng quat nhu sau: 2NaNO, + H3SO, —* HNO: + Na.SO, HNO; + Na,SO, —» NO’ + H,0 + HSO xO-n + NO’ + HsOo; —> x{O- NO + H,SO, X =OH.NR; San phdm two ra trong trudng hop nay thudng chi yéu 1a déng phan para. 2.11. MOT SO Vi DU CU THE VE SAN XUAT THUGOC Phan ting nitro hod dug duge sau day 1a mot s6 vi du dé: tig dung kha phd bién trong qua trinh tong hop hos 2.11.1. Téng hop paracetamol Mét trong cac phuong php diéu ché thuéc ha nhiét paracetamol (p-acctamidophenol la nitro hod phenol bang hén hop nitrosunfuric dé duge hd hop déng phan ocio- vi para-nitrophenol, sau dé cat kéo hoi nude dé cat laly ecio-nitrophenol (déng phan pure nitrophenol duge két tinh ra tit phan con lai cua qué trinh cit ko), Déng phar p-nitrophenol duge khit hod bang natri sunfua dé cho p-aminophenol. ké dé hop chai nay duge acetyl hod bang hén hop axit axetic — anhydrit axetic dé duge sin phir p-acetamindophenol (paracetamol). OH oH OH or H uNoytt,so, cr NO} oO ‘beOH OH gu 3 NaS AcOH oO NO, NH 3 NH-COCH, paracetamol 2.11.2. Tong hyp mebendazol Thuse giun mebendazol duge Wng hgp tir nguyen ligu ban dau [i anilin hoac acetanilid. Trude hét anilin duge benzoyl hod trong xtic tic ZnCl, wen co sé phan ung Friedel-Crafts. tiép dé 1a thuy phan dé duge 4-aminobenzophenon. hgp chat nay duge nitro hod véi tac nhan axit nitric 65% trong anhydrit axetic thu duoc 3-nitro-4-amino- benzophenon. Tiép dé khu nhém nitro thanh amino bing amoni clerua v duge 3.4-diaminobenzophenon. cudi cig [2 ngung tu dan x cacbometoxixyan amid dé duge mebendazol. bot sat thu t diamin nay véi NH, _CiH,COCUzZnCs 2 mo NH, | HNOJACO- Nis CoH es Cal HC xo. oO NC-NH-COOCH; o N — ox nN CoH “x7 NH-COOCH ii | oO H mebendazol 2.12. Vi DU Vé. CONG NGHE SAN XUAT NITROBENZEN 2.12.1. San xuat nitrobenzen bang cong nghé gian doan Phuong trinh phan ting Ol + HNO,/H.SO, —> o™ Dae trung ciia nguyén liéu va san phdm: ~ Benzen li chat lng khong mau. 6 mai dae biét, S6i 6 8O"C. néng chay 6 5°C, trong 6 20°C 14 0.879. Ba hoa tan trong nude 0.0747 ~ la chat doe gid wi MAK 1 5 mg/m’ - Nitrobenzen 1a chat long khong mau. dé mot thdi gian urd thanh chat long co mau ving nhat. soi 6 211°C, chay 6 5.7 °C. ty trong & 20°C 1a 1.222. Hoa tan trong 40nude 0.19%. Dé chung eat cuén theo hoi nude. it hoa sunfuric: 1a chat doc gid tri MAK 1a 3 mg/m’. an trong hon hgp axit nitro- Chat lugng nitrobenzen cong nghigp: hi lugng 95.0% t¥ treng 1,204 + 0.009 diém dong dac +4°C. ham lugng nude 1,0%, ham lugng benzen 1.5%. nhung chat khac khoing 2.0%. axit hoac kim chita t6i da 0.3% n pham phu trong san xual 1a dinitrobenzen. Cong nghé sin xudt: 1) Cong nghé gidn doan nitro hod benzen So dé qué trinh cong nghé gidn doan nitro hod benzen duge minh hoa trén hinh 2.1 yo - rs =o axit nitrosunturic ce | 4 8 Es a4 - ! ) axit sunturic axit nitric benzen axit dé ding nitrobenzen Hinh 2.1. Cong nghé gidn doan san xudt nitrobenzen: 1. thiét bj chun bi hén hgp axit; 2, 3, 4, 6, 8. cae binh dong, 5. thigt bj nitro hoa kiéu Hough: 7. thiét bi xir ly hén hap phan ting (phan pha, rita)Hon hgp axit nitrosunfuric duge diéu ché ra trong thiét bi cé thé khudy va lam lanh J. Cho vao thiét bi nay luong nuéc, axit sunfuric, axit nitric can thiét thong qua cdc binh dong 2, 3, sau dé dugc dua lén binh dong 4 va chuyén vao thiét bi nitro hoa 5. Benzen tit binh dong 6 dugc dua vao thiét bj nitro hod 5. Sau khi phan img, hén hop duoc chuyén qua thiét bj khudy 7 dé phan pha nitrobenzen va ria. Tu day pha axit di ding va nitrobenzen duoc téch ra. Lugng axit di ding mot phén duge hoan nguyen sit dung lai qua thiét bi dong 8. Pha nitrobenzen duge trung hoa v6i dung dich NayCO, va nuéc thu duge nitrobenzen thd, sau khi cat tinh ché thu duge nitrobenzen k¥ thuat. Nitro hoa: nitro hod benzen duge thyc hién trong thiét bi nitro hod kiéu Hough (xem hinh 2.2). Hinh 2.2. Thiét bi nitro hod kiéu Hough: 4, 2. khoang khudy tron; 3. c&nh khudy tuabin; 4.16 thao day; 5. 16 cho hydrocacbon va axit vao. bj nitro hod 3.600 kg axit da six dung (thanh phan: 2.3% HNO,, 83% H,SO, va 14,7% HO), sau d6 lam néng lén 50°C, trong vong 0,5 gid cho 4.000 kg benzen vao, sau dé 9.320 kg axit nitrosunfuric vao (thanh phn 36% HNO, 63% H,SO,, 1% HO) thai gian cho hén hop axit vao kéo dai 1 gi’. Trong qué trinh nay voi vige lam lanh duy ti hén hgp phan ing 50 + 60°C sau dé dua din nhiét 46 len 90°C va duy tri nhiét do nay trong vong 2 gid. Néu qua trinh nitro hod két thic (theo déi bing ty trong cita pha hiu co hodc ham lugng HNO, trong pha nuéc) thi dem xir ly tinh ché. Xit ly tinh ché: Hén hop phan ting duc chuyén vio thiét bi xit ly dé phan pha va rita 7 dé yen 12 = 14 gid, sau dé tach pha. Pha dudi la pha chia axit 44 ding dugc théo xuéng cho vio thing chia. Pha trén IA pha hitu co chil yéu 1a nitrobenzen duge rita bing nude néng 40 + 45°C, sau d6 rita véi dung dich Na,CO, loang va cudi cing ra lai bang nude, thu duge nitrobenzen thé. Higu sudt dat 98 + 99%, nitrobenzen thé nay dugc cat lai thu duge nitrobenzen ky thuat. Vige cat truée hét cho thém nude dé cat loai benzen ra theo hn hop benzen — nudc dang phi, sau dé cat chan khong dé thu nitrobenzen. 422.12.2. San xudt nitrobenzen bang cong nghé lién tuc C6 nhigu cong nghé lign tye nitro hod benzen dugc céng bé, sau day 14 mot trong 36 d6, So dé cong nghé duge minh hog trong hinh 2.3. Hén hop nitrosunfuric c6 thanh phiin 63% HNO,, 19% H,SO, va 18% H,O. Thiet bj nitro hod 1a mot loat céc thiét bi duge lap néi tip nhau. Ty céc thing chita ] duong lugng mol benzen va axit nitrosunfuric duge lién tuc chay qua céc Iu long ké 2 vio he théng thiét bi nitro hoa 3, 4, 5. Véi vigc lam lanh duy tri nhiét do 35 + 40°C & thiét bi 3, 45 + 50°C o thiét bi 4 va 55 + 60°C thiét bi 5, tigp d6 cho qua thap tach pha 6. ‘Tir day pha hitu co va pha nude duge tach ra. Pha hilu co lin tye din ra & phfa tren con pha nuéc & phia dudi thiét bi 6 duge hoan nguyén quay tré lai dé sit dung. 1 1 2 2 pha hau co nilrobenzen 55 60°C Hinh 2.3. Nitro hod benzen cong ngné lién tuc: 1. thing chéa 2. luu wong kg: 9. 4 5. cac thié* bj hitfo hoa; 6. chiét tach, phan pha. C6 mot cong nghé nitro hod lién tuc pha hoi theo phuong phap Othmer dure mo ta niu sau (so dé cong nghé xem hinh 2.4); Axit nitric néng d@ 61% 6 thiing chita J duge bod hoi trong thiét bi béc hoi /0 sau d6 hoi axit nitric dugc cho vao c6t thép nitro hod 3, déng thoi tir thing chita benzen 2 benzen sach va tir thiét bj tach pha 5 benzen thu héi duge dan cho vao cot thap nitro hoa 3. Qué tinh nitro hod duge xay ra qua su tip xtic ca benzen va hoi axit nitric trong th4p dia cé mi.Trén dinh thap hén hop ra c6 d6 s6i 72 + 78°C duge ngung tu & sinh han 4 va tach pha & binh tach 5, benzen tach ra 6 day duoc hoin nguyen lai thap 3. Sin phdm day thép dugc cho vao néi béc hoi 6, sau dé chay qua thiét bi tach pha 7. Pha nuée chifa axit nitric néng 49 60 + 68% dude hoin nguyén lai thap phan ting 3 nhir 43may bom 9. Pha hau co duoc chuyén qua thdp cat 8. O day cat loai benzen va axit nitric khdi nitrobenzen & tren 118°C, nitrobenzen duge lay ra 6 day. 1 Nitrobenzen 9 Hinh 2.4. Sdn xudt nitrobenzen theo cong nghé lién tuc cila Othmer: 1. thing chita HNO; 2. thing chifa benzen: 3. thap nitro hoa; 4. sinh han; 5, 7. binh phan pha; 6. néi béc hi; 8. thap ct; 9, may bom; 10. thiét bi bc hai 44Chuong 3 SUNFO HOA 3.1. DAI CUONG Sunfo hod fi m@t qué trinh hod hoc dua nhém sunfonyl (SO,H) vao mot hop chat hitu co: R-H —> R-SO3H Qué trinh dua nhém sunfonic vao m9t hgp chat hitu co c6 thé thuc hién truc tigp bang mot phan img thé hoac phan tng cOng (hay con goi 1a sunfo hod tryc ti€p) hoac bing phan tmg oxy hod nhém chia Iuu huynh bac thap thanh sunfonyl (goi 1 sunfo hod gidn tiép). Trong pham vi chong nay chiing t0i chi dé c4p t6i sunfo hod truc tigp. Theo quy dinh dan chat sunfonic 1a chat c6 nhém SO,H gan truc tiép véi cacbon cita hgp chat hydrocacbon bing lien két C-SO3H, qué tinh nay con goi [a qué trinh C-sunfo hod. Céc hop chat cé nhém SO3H gan véi oxy thi thuge loai este cia axit sunfuric hay cdn goi I sunfat va qué trinh hod hoc nay 1a qué trinh O-sunfo hod. Néu nhém SO,H gan vao nito thi hgp chit tao thanh goi ld axit sunfamic va qua trinh 46 goi 1a N-sunfo hod C-sunfo hod O-sunfo hod N-sunfo hod CH,-CH,-SO;H CH,-CH,-OS0,H CH,CONHSO;H axit_etyl sunfonic etyl sunfat axit_axetyl sunfamic Sau day 1a danh php hod hoc mot s6 nhém hgp chat hitu cg chia Iw huynh: R-SO,H + axit sunfinic (axit ankyl sunfinic) R-SOH : axit sunfonic (axit ankyl sunfonic) R-SH —: mecaptan (ankyl mecaptan) R,SO —: sunfoxit (diankyl sunfoxit) R,SO, :sunfon (diankyl sunfon) R-SR_—: ete (diankyl ticete). 3.2. CO CHE PHAN UNG SUNFO HOA Cling nhu trong qué trinh nitro hod ta cn phan biét hai loai co ché phan tng khac 45nhau gitta sunfo hod cdc hop chét nhan thom va céc hgp chat hydrocacbon no mach thing vi hai trudng hop nay co ché phan tmg xay ra hoan toan khée nhau, diéu kién phan img cing khdc. 3.2.1. Co ché phan ing sunfo hoa cac hgp chat nhan thom Sunfo hod cdc hgp chat nhan thom véi tae nhan axit sunfuric 1a mot phan tng thé i dign tir Sg, nh6m thé i dign tir chinh 1a SO,. Nném SO, duge sinh ra tir phan tng di li cia axit sunfurie theo phuong tinh duéi day: 2H,SO, == _H,0"" + HS,0;°" == H,0" + HSO,"7 + SO, 3H,SO, == HSO,;" + H,0™ + 2HSO,"? Va chinh SO, hoac HSO,'* nay nhu téc nhan 4i dién tir tén cong vao hé théng dién tir = cia nhan thom dé tao ra phan tir luGng cuc kiéu phiic o va sau dé voi viéc dich chuyén proton phan tit sunfonic én dinh duge tao thin. SO, H — SO3H Cang cn phai nhan manh thém vé SO, trong vai trd 1A mot tic nhan di dien tir nay: Do phan td SO, c6 nhing Li¢n két ban phan cyc cita né ma né hoat dong nhu mot phan tt phan eye. 19 1 BiH) 8) Hep SO = S05 101 &(-) 3. Co ché phan ting sunfo hod déi voi hydrocacbon mach thang Khée véi cde hydrocacbon thom, eéc hop chat hydrocacbon no mach thing khé thyc hign phan tng sunfo hod. Trong thyc té héu nhu khong thé ding axit sunfuric dé lam tic nhan sunfo hoa d6i véi cdc hgp chat hydrocacbon no mach thing vi sunfo hod bang tdc nhan nay cho hiéu suat rat thap. Mudn tao hgp chat sunfonyl & hydrocacbon no mach thang ngudi ta thudng phai thyc hién sunfo hod & nhiét 46 cao hode xtic téc bang 4nh séng v6i hén hgp khi SO, va Cl,. Lic nay phan ting xay ra theo co ché thé g6c ty do, bing phan ting day chuyén. Cl + 4nhséng —> cl + cr Khoi mao CyHo + Cl = —> CE, + HCL } - Day chuyén CyHier + SO. > C,Hone1802 (nhanh)CyHansr + Clp = > CHa Cl + CI tam) Day chuyén CiHope180) + Cle —> C\H_,,80,C1 + CI" oe ch } Két thie CyHaaiSO] + CI” —> C,Hag)S03Cl 3.3. CAC SAN PHAM PHU Vi hai loai eo ché sunfo hod & hai loai hop chét hydrocacbon khéc nhau cing knde nhau nén sin phim phy tgo ra tir phan ting sunfo hos hai loai hgp chat nay cing khdc nhau. Doi vdi sunfo hod cdc hop chat thom theo cg ché thé 4i dign tir (S-) sin phim phy {4 san phim thé hai hoac ba hydro bing hai hoac ba nhém sunfonic hodc IA cae déng phan vé vi tri (acto, para, meta) cia nhém sunfonic. Con trong sunfo hod cdc hyp chat hydrocacbon mach thang thi sin phém phu la ce din xuat sunfo cé mach cacbon ngiin hon hoac cling mach cacbon nhung cae vi tri khdc nhau hodc dan xuat polysunfo. 3.4. CAC TAC NHAN SUNFO HOA Tac nhan sunfo hod c6 nhiéu loai nhung chung qui lai thudc hai nh6m co ban 1a cae din xuat ciia SO, va cia SO. 3.4.1, Cée tac nhan sunfo hod 14 dan xuat cia SO3 3. SO; nhuc la mét téc nhén sunfo hod G6 thé hoi SO, & dang monome, nhung & thé khdc thi né tén tai & ba dang khac hau; dang y 18 trime cila SO; thé l6ng co d6 néng chay 16,8°C; dang B 1a polyme ciia SOx thé rn c6 nhigt do thap, chy & 32,5°C va dang @ la polyme cia SO, thé ran co nhiet do néng chay 62,3°C. Gf oR —0-$-0-8-0-s oO oO oO Dang B +a a. dai hon B (ng > np) Khi chug cat oleum thi ta thu duge lu hujnh trioxit & thé Iéng gém khong 90% trime (dang y) va 10% SO, monome. SO; monome dé trong khong khi, nhiet do thudng sau mét vai gid sé chuyén sang dang P va c. Qué trinh nay nude 1a chat xtc tdc 47Dé ngan can qué trinh chuyén dang ké wen ngudi ta cho thém xtic tc 1a botrioxit, bo, uu huynh hoac photpho. Dang SO, dé sunfo hos 6 Igi 1a sin phim phy (nuéc) khong tao ra, khong cén ding thiia SO, tinh ché dé dang, nhung vi SO, 1a tée nhan sunfo hoa manh nén dé gay ra hién tugng than hoa. Vi vay khi sit dung thu’ng phai pha lodng véi dung moi nhw 'SO;, CCl, hodc dicloetan 3.4.1.2. Hén hop SO; va nuée nhu lé mét tac nhan sunfo hod SO, v6i nuéc tén tai & nhiéu dang én dinh: dang hai phan tir SO, ngam mot phan tir nude goi 1a axit pirosunfuric, dang mot phan tir SO, ngam mot phan tr nue goi Ta axit sunfuric, dangmot phan tir SO, ngam hai phan tir nuéc goi 18 axit sunforic mono- hydrat. Trén day 1a cau trtic céic dang d6. ap 0 g 57 at 0-H Q. -H H-0, 0-H 0=S=0 OQ o-H 78x aN sf Oo ‘O-H H-O° “o-H SO3 a So annydtit S03. H,0 H,SO,. H,0 2803 .H,0 axit sunfuric axit sunfuric monohydrat axit pirosunfuric pC = 10,5°C DC=9,5'°C (45,3% oleum) oo (84.8% H,SO.) Ngoai ra luu hujnh trioxit t6n ta If giai i sao axit sunfuric héo nuée: duéi céc dang 3 va 5 phan ti nude, day 1a diéu SO;.3H;,0 SO3.5H,0 (H,S0,.2H,0) (H,S0,.4H,0) wihydrat pentahydrat 74,1% H,SO, DC = 26,7°C 57,6% H,SO, DC = 25°C 6 nhige do thép céc dang hydrat néu trén dn dinh, bén ving, nhung nhiet do ler cao thi bj phan huy, & 450°C thi hoan toan phan huy thanh nude va SO3. Vay axit sunfuric bao g6m mét khai niém cia SO, + nH,0. Con oleum 1a dung dich SO, hoa tan trong axit sunfuric 100% 6 nhiing nhiét de nhét dinh, SO, nguyén chat khong ding dé sunfo hod vi tac dung kha ménh hier, 46 chéy chat hitu co gay than hod. O nhigt do thudng SO, [a chat rin, ket tinh, khd thay tdc vi lé 46 nén trong c4c qué trinh sunfo hoa thuing ding oleum. Hai loai oleum ha duge ding 1a olcum 20% va 65% vi cdc oleum khac ty le nay déu bi ket tinh khé tha tac, Hign tugng nay duge gidi thich bing biéu dé biéu dign dé chay va ham lugng pha tram SO, cha H,SO, va oleum. 48H,S,0; axit pyrosunfurie y 10 20 30 40 50 60 70 «80 90 100 %S0, ty do Vay lay nhing loai oleum & khoang ty 1é 20% va 65% sé ludn ludn 6 thé long dé thao tdc. Thyc té hay ding loai 20% dé sunfo hod. 3.4.1.3. Phite chat cia SO; v6i hop chat hitu co Gin day 48 sunfo hod nhiing chat hitu co dé bi pha huy béi axit sunfuric (nhu sunfo hod céc hgp chat 66 day néi doi, néi ba) nhing chat ky axit va dé sunfo hod mot céch nhe nhang, ngudi ta ding cdc téc nhan c6 SO, két hop voi dioxan, thioxan, pyridin, amin bac 3. R, 7 > O * od bso, ‘ VY S080; N R,—N— SO. — 1 27 > 50, Ry f™ ™. 08-0 0--SO; O38--S S-+ SO, 3.4.1.4. Cée halogen sunfonic axit Céc halogenua sunfonic axit (HSO;Cl) nhu 1 mét chat sunfo-cloro hod tign Igi Ding axit clorosunfonic dé sunfocloro hod phan ting xay ra nhe nhang, khéng dai hoi nhiét 46 cao, chinh vi vay sin ph4m sach, tinh khiét hon la ding axit sunforic hoac oleum. Axit clorua sunfonic dugc ding nhiéu trong san xudt cdc sunfamit. ArH + CISO,H —> Ar-SO,0H + HCl Ar-SO,OH +CISO,H = Ar-SO,Cl + H,SO, ArH + 2CISO;H —> Ar-SO,Cl + H,SO, + HCl 493.4.1.5. Axit sunfamic (NH,-SO;H) nhu la tac nhan sunfo hod H,N-SOH c6 do axit manh nhu H,SO,. Trong sunfo hod H,N-SO,H cé tae dung hu phite hyp amin-SO;, nhung khéc véi phite amin-SO, 1A né ding duge trong dung dich khan nuGc & nhiét dé cao, nd cé thé sunfo hod vinylbenzen thanh axit phenyl-vinyl sunfonic. CsH;-CH=CH, + NH,SO.H — C,H;-CH=CH-SO,H + NH; 3.4.2. Céc tée nhan sunfo hoa thuge dan chit ciia SO, (nhém 2) 3.4.2.1. Cée mudi sunfit, bisunfit Céc loai téc nhan nay chi ding trong céc trudng hgp khi khong ding duge axit sunfuric hoac oleum. Vi du: ding trong viée digu ch€ céc mudi natri sunfonat cla céc hop chat mach thing c6 s6 cacbon khé 16n di tir din xudt ankyl halogenua. Trong truéng hgp nay phan ting xy ra theo co ché thé 4i nhan (Sy). R-X + Na,SO,—> R-SO,Na + NaX Céc halogen mach thom chi té dung duge v6i mudi natri sunfit hoac bisunfit néu trong nhan them cé chifa nhém NO, 6 vi tri o- hoe p- va lic nay phn ting xy ra theo co ché thé di nhan. SONa o™ 450) o" 3.4.2.2. Hén hop khi SO, va Cl, SO,Cl, nhu la m6t tc nhén sunfo-cloro hod Dé sunfocloro hod cdc ankan, cycloankan, arakan ding SO,Cl, du6i tac dung ciia nh sng. Trong cong nghiép c6 thé thay SO,Cl; bing hén hop khf SO, va Cl, R-+H + SO; + Cl, “8, R-S0,Cl + HCl 3.5. TAC DUNG CUA XUc TAC VA CAC CHAT PHU GIA Trong qué trinh sunfo hod ¢6 mot s6 chat c6 tac dung lam tang kha nang ciia phan ting, lai cé mot s6 chat khée chi phéi ti vi trf hinh thinh cia nhém sunfonic, cing chinh vi thé vige sir dung chat xtc tdc hodc chat phy gia 1A mot digu kién o6 tinh kinh té. Sau day I& mot sé vi du cu thé. 50Thuy ngan: N€u sunfo hod antraquinon theo cach binh thudng thi héu nhu ta ct nhan duge déng phan B, nhung khi cé mat thuy ngan hose musi clia né Lim xtic téc th héu nu nhan duge toin bd sin phim véi déng phan a. Trong nhiéu truéng hop thuy ngan hay mudi cia né gitip cho viéc sunfo hos xa ta dé dang hon, thuc hién & nhiét 49 thip hon so véi khi khong ding xtic tac nay (Vid khi sunfo hoa pyridin hoje ankylpyridin). Vanadi: Trong viéc sunfo hod benzen dé duge din xuat disunfonic, vanadi pentox lam tang kha nang phan ting mot cach ro ret mA khong chi phéi tdi vi tri nh6m thé. Pyridin: Lam tng kha nang phan ting cita qué trinh sunfo hod céc hop chat xeto mach thing, cdc anhydrit vA cdc axit béo & néng d6 pyridin 1a 0,01%. 3.6. DUNG MOI Cae dung méi hay sit dung trong phan ting sunfo hod thudng 1a ban than cht dang dé sunfo hda, SO, hod léng, cloroform, tetraclorua cacbon, cdc chat tro véi té han sunfo hoa va hoa tan duge cdc chat phan ting. 3.7. DIEU KIEN CUA QUA TRINH SUNFO HOA Phan ting sunfo hod 1a qué trinh phan ting thuan nghich Ar + H,SO, == Ar-SO,H + H,0 Dé chuyén can bang vé phia phai thudng ding Iugng H,SO, (tinh ra néng 46 SO. thita gap 2 + 5 lan. Phan mg sunfo hod 1a loai phan tng to nhiét (exothermic). Nhié lugng tod ra bao g6m hai phn. Mot phén do nhiét phan ting, phan khdc do nuéc tg0 1 trong phan img pha loang axit sunfuric. Khi ding SO, dé sunfo hod thi trong phan tng nudéc khong tao ra, nén phdn nhié nay khong cén tinh téi, nhung-vi do nhiét phan ting qua 16n gay nén hién tugng tha hod, lam chay mat mot phéin nguyén ligu. Khi ding axit sunfuric 1am téc nhan sunfo hod thi nhiet tod ra it hon vi ban tha qué trinh gidi phéng SO; tir axit sunfuric 1a qué trinh thu nhiét vi vay lam cho luon nhigt toa ra trong phan tng giam di. 2803.H,O —* 280; + H;0 AH= 116 kcal/mol SO;.H,0 (H,SO,) —* SO, + H;0 — AH= 20,26 kcal/mol 803.2H,0 (H,S0,.H,0) —* SO, +2H,0 AH = 26,96 kcal/mol Thuéng khi tang nhiét 46 phan ting lén 10°C thi tc do phan ung tang lén 2 = 2, lin nhung kha nang than hod tao san phdm phu cing tang én nén thudng phai thy hign phan ting 6 nhiét do khong cao.‘Trong qué trinh phin tng néng do H,SO, sé ngay mét gidm dn, mot phn vi né tham gia phan tng tao ra san phim (Ar-SO;H), phan khac bi nuéc tao ra trong phan img pha loang. Két qua lic déu khi néng 49 axit sunfuric cdn cao thi phan tng nhanh sau dé cham déin vi dén mot Ic nao dé thi ngimg han khong thé tham gia phan ting duge nia. Giéi han néng 46 SO, ma 6 dé phan ting khong xAy ra duge nita goi gidi han 46 Ia pi-sunfo hod viet tit 1a 7. Khi thyc hién phan ting ta céin phai biét gid tri nay, gid tri m phu thudc vao ban chat nguyén ligu dem sunfo hod va nhigt d9 thuc hign phan ing. Vay méi nguyén litu khéc nhau cé mot gid tri x & nhiét dO tuong ting cia n6. Vi dy gid tri cla x khi sunfo hoa benzen 6 nhiét 46 60°C 14 66,4 va naphtalen 1a 56 ( 60°C) va 52 (& 160°C). Vay gié tri cia x khi sunfo hod benzen 1a 66,4 c6 nghia IA gi? Diéu 46 c6 nghia 18 khi néng 46 SO, trong hén hgp phan ting gidm xudng 64,4% (tinh ra H,SO, 1a 66,4 : 0,8164 = 81,3%) thi khong thé tao ra san phdm benzen sunfonic nia. Vay trong qua trinh thuc hién phan dng cdn phai duy tri hén hop phan img c6 néng do SO; lu6n luon phai 16n hon gid tri x cia né (phai lén hon 66,4 % SO, hoac 81,3% H,S0,). Khi biét gid tri x sunfo hod cia mot chat 4 mot nhiét dé nao 46 ta can tinh Iugng SO; cho dit 4é phan tmg duge thyc hién ho’n to&n. Trong thyc té long H,SO, cén thiét sunfo hoa 1 kmol hgp chat hitu co duge tinh theo gid tri x nhu sau: 80.(100 —n) a-n . X= trong dé: X 1a 86 kg HySO, cfn tinh; " ala néng dO ban dau cla SO, trong téc nhan sunfo hod dem ding; ‘m: gid tri x sunfo hoa cita chat hitu co nguyén ligu (H,SO, 100% cé gid tri néng do SO, 14 81.64%). ‘Tir cong thifc trén ta iit raz - Chat nao cé gid tri m nhé thi dé phan ing. - Thue té cho thay cdc chat hydrocacbon nhan thom cé chita nhh6m thé loai I thi cé gié ari x nhé, ngugc lai cé chtfa nhém thé loai II thi o6 gid tri x 1én hon. ‘Tom lai hai yéu t6 nhiét do va néng do SO, cila t4c nhan sunfo hod anh hudng lér dén hiéu suat cia sunfo hod. 3.8. PHAM VI SU DUNG CUA PHAN UNG VA UNG DUNG CUA CAC HOP CHAT SUNFONIC Phan tng sunfo hod cé thé thuc hién trén nhiéu loai hgp chat cd mach thing mach vong va nhan thom, nhung *hdi loai hgp chat lai cé su khdc nhau, vi vay ta lar lugt nghién cu viée sunfo hod timg loai hgp chat 46. 52a) Sunfo hod cdc hop chat mach théng: Nhu céu vé hop chat sunfonat trong ky nghé ngay cAng 1én cho cdc nganh cong nghé phdm nhuom, bot giat (chat nhdi hod, chat lam gidm stic cang bé mat, chat tao bot). ~ Cie déng ding ca hydrocacbon no mach thang khong thé sunfo hod duoc v6 H,SO,, ma phai sunfo hod truc tigp vi oleum 6 thé khi theo co ché thé géc Sp. - Da sé cic sunfonic cia hgp chat mach thing cé mach cacbon Idn thudng dug digu ché tir hop chat halogenua tuong tng cia né bing phan tng cia Strecker (nung ankyl halogenua véi mudi natri hoa amoni sunfit). R-X + Na)SO,{(NH,),S0;] —* R.SO,0Na + NaX R-X + (NH,),S0; —* RSO,ONH, + NH;X X = halogenua - Xeton hogc andehit mach thing cé thé phan ing dugc véi oleum dé tao ra mono disunfonic axit R R \ 1 R-CH,-CHO i, HqSOsH + CSO3H), CHO cHO ~ Axit hftu co mach thang téc dung véi axit clorosunfonic tao ra a-sunfoaxit hit co (a-sunfo cacboxylic axit). CH)-CH,-COOH + CISO,0H —> CH-CH-COOH + HCI S0,0H - Axit hitw co véi oleum sé tao ra c-sunfo-axit sau dé decacboxyl hod tao ri sunfonic axit. ’ R-CH,-COOH + SO; —» R-CH,-COOSO;H —> — ie R-CH-COOH 2s, R-CH,-SO,H SO,H - Céc hydrocacbon khéng no, céc déng ding cila axetilen cé kha nang cong hoy véi H,SO, va SO; dé tao ra hgp chat sunfonic. H. H “C=C7 + 4803 —>