Luận án phó tiến sĩ khoa học hóa học phản ứng trime hóa vòng arylizoxianat bằng phương pháp xúc tác chuyển pha

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BQ GIAo Dl)C vA oAo TAO TRUONG O~I HQC TONG HQP TP. He CHI MINH 1ted g'~ ., , " PHAN lJ'NGTRIME HOA VONG ARYLIZOXIANAT BANG , " K PHUONG PHAPXUCTACCHUYEN PHA& THAM DO vAl (mG DUNG . ., . IZOXIANURAT CUA 2,4 A , - TDI "" ,., CHUYENNGANH HOA LY-HOALYTHUYET ~ ,., MA SO 1.04.04 TOM TAT A ~ ~ ~ - ~ LU~N AN PHO TIEN SI KHOA HQC HOA HQC THANH PHO HO CHi MINH-1992 u' 1. 6-'~ N Lu{m lm dU'Q'c holm thanh t1;\i PhOng Hoa Ly. Hihl cO' cua Trwng l.>~i hQc Tbng hgp Thanh phf> H6 Chi Minh. NguOi huVng din khoa hoc : 1. GSTS CHU PHAM NGQC SaN 2. PTS LE TH1 NffirT HOA NgWi Dl$1 x6t : - Thtr nhAt : - Thtr hai : Ca quaD nhtn x6t : Lu~n an duvc hQpt~i Tru&ng bao v(? tnrac H{li d6ng D~i hQc Tbng hgp Thanh gio-. ngay thfmg chiim Lu~n fm Nha mrac phf> H6 Chi Minh VaG Hic Dam 1992. Co th~ tim dQClu~n lm nay t~i : . Thu vi~n Khoa hQc Tbng hgp TP. H6 Chi Minh. . Thu vi~n truo-ng D~i hQc Tbng hgp TP. H6 Chi Minh - I - I - TONG QUAN TAllI~U : Phlul (mg trime bOa vong arylizoxianat t~o thanh nhi'mg hgp chAt izoxianurat b~n nhi~t. ph\! thuQc chit y~u VaG Io~ xiic lac va co ih~ vi~t thee phU'O"llgtrinh phlul (mg sau : 0 II C """-N/ Ar 3 Ar NCO 'N/ Xuc lac ;> d O~ Ar b 'N/ I Ar ~O , . .-- ,~..,..._. !,: Ia 16.5 keal-moH (17J. b - Xiic tac 1a bazu cua N. P. As. Sb Cae lac giA Sorokin va dOng nghi~p [31] eho rAng a giai do~n khoi maD cUa phlin (mg co S\l tiic kieh than h~eh eua xUc lac ch~ng h~ R3N. ireD cacbon cua nhom NCO t~o thanh mQt ion IuO'ng C\rc phan ly mQt philo hay loan philo dwi d~ ion hrcYngtinh (zwitterion) nhu sau: R3N + O=C=N-Ar ~ R3~-C-~ II I 0 Ar Ion Iu6'ng tinh trung gian co tinh than h~ch t6t d~ pMt trilm pb8.n (mg. Phan Ung xay ra eMm poliizoxianat. LU'Q'ng xUc lac izoxianat ban dAu. va eang cMm sir dl,lllg ciing kha ubi v6'i hgp ch5.t l&n so v6'i lU'Q'ng - 2 - . Loi.iixuc lac mly co th~ tang hoi.itbAngcach su d\lIlgchdt dimg xUc lac nh\!" hQ'p chAt cpoxi. loti xUc tAc [32J. , HQ'P chdt dbng xUc tac' epoxi amin tarn ti.iO thanh m(}t ion lwDg R3N + CH2-CILR' "01 ~R 3 N@-CH 2 ~ cacbamat ho~c chAng hi.iD. lac Ulll nh\!" sau +b R3N m(lt baza khic d\lIlg vao cimg xUc lac : GHz_CH_R' "...01 -~ -CH-cP I R' Niiu co s\! hi~n di(!n cua dung m6i luUng C\!C phi proton. no se an d!nh ion lwng tinh trung gian nay va do do tang v~ tOc phan \mg. c - Xuc tac Iii h{Yp chAt cO' kim : H<;rpchdt cO' kim co th~ chia thanh hai nhom [14J : . Nhom I. co di.iDgchung 1<1MX (M kim loi.ii lien kiit ; -x : -OR, . Nh6m II. la ancoxit. : kim loi.ii ho~c nh6m xuAt c6 -SR, -NR) DOi vo-i xuc lac I1hom I. d~ tang hoi.it tinh cua n6 phcli su d\lIlg dung m6i lwDg cvc phi proton nh\!" Qimetyl sunfoxit (DMSO) ho~c N,N-Qimetyl fomarnit (DMF). Con nhom xUC lac II, chi cAn su d\lIlg mOt nbng dO nha cua DMF ho~c DMSO la du diJ tang hoi.it cua xUc lac nay. Xuc lac cua I1hom I cODg vao n6i N=C cua -N=C=O ti.iO thanh mOt san phAm c{mg co nhom cacbonyl chAng hi.iD [l1J 0 II BU3Sn-O-SnBU3 + Ar-N=C=O --7 Ar-N-C-O-SnBU3 I SnBU3 Nguyen tu kim loi.ii lien ki!t v&i nitO' lam tang tfnh bazO' cua nitO'. HQ'P chdt c(}Dg nay co mang tinh than hi.ich (dAu N) hun izoxianat ban dAu va co th~ gia tang v~n t6c phan irng ~Ung vo-i hQ'P chdt phirc ti.iP than di(!n tu ti.iO thanh b&i xUC lac nhom II va izoxianat. V~ m~t hinh cua - NCO biiin tir di.ing ti.iP chUng sp sang sp2 lam d~ dang s\! ti.iOphuc v&i xuc tac nhom II. ni!u co [15J. h9C, cacbon - 3 - D6i v&i xUc lac cua nhom II khOng c('mg tn,rc ti6p vao - N=C=O nhu nhom I. tU'O'nglac gifra ion kim lo~i v&i nguyen tir am w9n N ho{\c 0 cua izoxianat lam cho cacbon cua - NCO cang thi~u di{m tIT hall. Dung m6i hrong c,!c phi proton DMF va DMSO co lac d\lIlg bn mrm ion hrong tinh hay chAt phirc t~p t~o thanh do lac d~ cua xuc lac nhom I va II leu - NCD. . M6i xUc lac cua tUng nhom nay co th~ duqc tang ho~t bftng cach sir d\lIlg kbt hQ-p v6i m~t xUc tac cUa nh6m khic cUng lov,i (k~t hqp nhom I v&i nhom II). Vi~c dUng h~ d6ng xuc lac ciing nhom. nhom I-I ho{\c nhom II-II. kh6ng co tac d~. D6i v&i nhom I co th~ tang ho~t bftng KI. d - Xuc tac 1ii mu6i hotic Oxit CUBkim lo{ti kiJm va kii!m th6 Trong trwng hqp nay. ngm'ri ta phai sir d\lIlg dung m6i lu&ng c,!c phi proton m~ nhu DMF ho{\c DMSO d~ gap phiin tang ho~t xuc lac vii boa tan d\r benzyl. alyl > > ankyl . Lo<;lixUc lac nay co th~ tang ho~t bftng hQ'p chit cacbamat t~o thiinh do lac d\lIlg cua mQt ru<;yuv&i izoxianat tU"O'llgirng. Tac d~ cua chAt dbng xUC lac cacbamat Iii gay hi~u irng earn phan c,!c trim nhom NCO bAng s,! t~o thanh lien k~t hiaro. - 0+ N = C 0- =0 I 0II H-N-C-O- S,! tang tinh than di~n tIT cua nguyen tIT cacbon cang \rU dai cho s,! lac kich than h~ch cua chAt xuc lac tren nhom NCO, phan irng pMt tri~n d& dang va v~n t6c phiin hidraxil irng tang e - Xuc tac 1ii muM amoni vo cO' va cua axil cacboxylic [21J. ho!)c pholphoni l(r cJ.p CUB Ho<;lt tinh cua xuc lac tuy thuQC vao tinh than h'.lch cua anion trung tam ho<;lttinh cua xuc taco N€!u co s,! thay th& nhom ankyl tren cation amoni chimg h'.lll bftng nhom hiaroxiankyl. ho<;lt tinh cua xuc lac sc tang rAt nhif!u. Nhom hiaroxil trim cation amoni se lac d\lIlg v&i izoxianat nhu sau [22J. - 4 , -tfi- I ~ -OH + ArNCO ~ I TuO'ng tg nhu tren. nhom uretan obng xUc Lac m~ clio phan Ung trime cgc tren nhom NCO. lam clio nguyen tu diii sg Lac kich than h~ch cua anion xuc -~ ~ -O-CO...:NH-Ar I t~o thanh nay se dong vai tro bOa vong izoxianat t~o sg phim cacbon cang ngheo di~n tu. U'U tac'vao -NCO. hbng ngolli va phan tich nguyen tb. l 3 @- NCO 10%NaCN. 2.57.Aliquat 336) Trime to {Xlong.khong dung moi :x - a K6t qui : Cac san phAro trime la bt)t trimg mjn. co k~t qua di~u ch~ vanh~ danh nhu sau : BANG1 C6H5NCO Therigian (phut) I2 Hieu suAt I (%) 97 Dim nong I 280 ch3.y (0Q Ph6 h6ng .~olli vKBr ( cm-l ) 1710; 1412 Ip- CIC6H4NCOm- CIC6H4N1m-CH3C6H4NC I I 2 I 97 I 318 1724 2 I ; Iz I 97 I 97 I 214 I 205 1400 1724 ; 1408 1710 ; 1414 ' I Phan ticl: nguyen to C21H1503N3 C21H1203N3C13!C21HIZ03N3Q3 C24H2103N3 71.00:4.17;11.36 54.40;2.59;8.87 54.74;2.62;8.81 72.07;5.21;10.241 1 CHN (%) ! ! I b - Bi~n luf,n 8 - : Ki!t qua cho thfly. phucrng phiip XTCP la mQt ph\lO'ng phiiP. r~t hero hi~u dOi v&i phan irng trime hOa vang arylmonoizoxianat. Nhung chUng ta phai cM y. khOng th~ tang v~t6c ho{ic hi~u su§.t phan (mg bAng cach vira tang nhi~t dQ vira tang nbng dQ cua mc laC va dbng thai chgn mu6i co tinh baw r~t m~ di! co san phAm trime slJ-ch duhbng ngo~i 2926 (\) CH~. : \) KBr (cm-l) 2278 (\) Ncd' 1593-1515 (\) Nhan thom). : 1716 (\) 1407 (\) cua swn c =0 cua vong trime) izoxianurat). Phi> cho thAy khOng co SJ,rhi{m di~n mill di{lc trung \) C=O cua vong dime a vUng 1785 cm-l [17. 18. 25. 30J va khong co SJ,rhi~n di~n cua polime m~ch thAng dugc di{lctrung bAng mill hAp thu a khoang 1660 cm-l [20J. . Tim hi~u dQ b~n cua 1 San phAro trime diI M~ trong chai d~y kin va cAt ky trong binh him khO v~ mAt ddn cac nhom NCO theo thai gian. SJ,r ki{!n nay cho thAy sau mQt thai gian da gift trong binh him khO. san ph1im tr& thanh khOng bOa tan dugc trong dung moi dll bOa tan dugc trime hIC d&u. Phi> hbng ngo~i cua ciIng mQt m~u san phAm. nhung dugc ch1;ly cach nhau - 10 hai tuhn. cho tht..y mOi dQ.c tnmg cua nhom NCO if 2278 cm' cling ng~n Jim va xuAt hi~n mt1i Nfl a vUng > 3400 cm '. ChUng to nh6m NCO dii m~t mi>t phAn d~ tao thanh cacbamat. 51,1'kj~n nay ciing dut sb Uic gia d1\ gin chu truUc day [8]. D~ co th~ phan Hch nguyen tt> san phAm bn dinh. ch(mg tai kh6a nhom NCO CUR1 bing MeOn ho~c glixidol. b - Bi(m lu{ln : Phlm (mg trime hoa vDng 2.4-TDI co th~ thl,l'c hi~n dlT chgn Igc cao va chi cho trime. Hi~1l suAt phan (mg ciing khn cao. Nhung cung khang Den keo dlli th<'ri gian qua 11Iu d~ trlinh kha nl\.ng phAn (mg CUR nhorn NCO a orIlla. Phan (mg khOng thb thl,l'c hj~n trang di~u ki~n khong dung mM vi. xay ra qua nhanh vii loa nhi~t rAt nhii;u. dAn dl!n Sl,l'hinh tMnll palime kh6ng tan do phlm (mg xay ra khang nh(mg iY nhom NCO para dbi vb-i OJ3 ms. cDn iY nhom NCO 0- orlha nfia. Dung moi kha tbt Iii. toluen. [rime khOng ta'n tach r<'ri kilOi mol tHrong phfm (mg. Vi~c co I~p san phAm dO'lJgian hern. 1 ciing khong b~n v&i th<'rjgian tuO'ng duerng nhu dibll ch/) trong dil!u ki~n dilng tuang. Co thb gifr 1 iY tqmg thlii dung dlch trong m(jt thai gian tucrng dM IAIl hern va sir d\mg dung djch nay db (mg d\lIlg trong vi~c ch~ t\lO vecni va chAt k~t dinh. 2.2 - Din xuAt cUll. 1 2.2.1 - Trimclylcllcbamal III CUB J 0 NOO a~~ N./ I &,C,- 0 ~ ""N ,~'NCO GY I ./ C+~ ~ ? 013 a~ a( 0 0 " . 0 ~! - C-;OI, N./ ""-N)0I 3cn 3on dung I, d 'hoan mol hru 2cua gio-d ./ b '" ~~O oP ~ y ~ ::' -Omlocoom> 1/ 013 la (96%) 0 ~ - 11 - !If Nh~n danh : Sim phAro la Iii mgt bgt trAng cSn ~. nhtr 1. co d~c trung sau day: - PhcS hlmg \) KEr ngo~ (em-I) khOng co tinh barn dinh : 3436 (\)NH ). 2960 (\) CH:3). 1708 (\) C=O cua vong trime). (\) cua swn izoxianurat), 1234 (\) CO- 0). 1418 Phi>eho thAy mill d~e trung eua nhom NCO {y 2278 eml dii mAt hAll. - Phan tieh nguyen tb : C3OH3009N6 C% H% N% Ly thuy€!t 58.25 4.85 13.59 Do dm.rc 58.23 4.80 13.22 2.2.2 a - - Dieu Triglixidyl cacbamat CUB 1 (Ib) ch~ hoa chAt glixidol Phim (mg dtrQ'c th'!c hi~n bfmg hai giai do{lIl !If Dieu ch~ dAn xuAt monoclo H2SO4 dd + 2NaCl I'i/:., .., c-;-~;'--,., ,';,:;<'t.,-,i.:.J ; Tlljf1iF--'P-' ! HCl dd) 2HClt + HClt :}(;j-'- I L---~~- + NazS°4 - 1200C ClCHZ-CHOH-CHZOH 3- cloro-1.2- dihidroxipropan ~ 10 gi& + CHZOH-CHCl-CH20H 2- cloro-1.3- dihidroxipropan DAn xuAt monoclo dm.rc co l~p bfmg each chung d.t phan do~n dwi lip suAt kern. Hi~u suAt Iii 50% vii dg s~ch cua san phAm d,!a tren phep ~ phan Cl va sAc ky khi Iii 96% co 90% dlmg phan 1.2 va 6% dong phan 1.3 [4J. !If Phan (mg dong vong dAn xuAt monoclo dtr&i dieu ki$n XTCP 120%K2C03. 1%Aliquat 336 ClCHZ-CHOH-CH20H+ CH20H-CHCl-CH20H "8Oml dietyl ete. heaD ItrU 4gi& h5n hQ'p dong phan 0.1 mol CH2-CH-CH20H ' / o -~- .._~~:_i_~5-i \ ~---~~: ~_.: cua glixerin 90 CH20H-CHOH-CHZOH : ,...---..-i"" glixidol (68%) j I : - b - 12 - Di~u ch~ Ib NCO ~ "3 013 0 0 ~ N/C'-N@NCO CI 1+ 0~ N ./ 30-1 -O-I-n-IOB C" 2/ _°"2 ~ 0 0 ~ dung moi cua J .. 0 ~ holmhru3 gi& !'.'B-C-OOI -CH-rJI 2 '2 r 0 II3C 0 0 @N/ NCO CH C 0 013 0 '-N.@lNlJ-C-OaI " 3 d o~ h N./ -aI-a', 2 ,I 0 . "'0 0 r81 ~~ . 3 TI18.n- (mg xay ra NIH- am 2 0 II 1b (937.) d~ dang va cl1ng khong cAnxu~ tlic. .do hidro linh d(Jng dla glLxi<1o1tile kieh vao nhom NCO eua 1 h,IO thanh nhfmg nh6m cecbamat. Hgp chAt 1b 10. m{jt triepoxi haa tan trong dung moi Ol3CN co kM filIng su d~g him nguy~n Ii~u di6n ehb ch[;t kbt diOO epoxi va chAt 6n dinh PVC [9]. . Nh~ndanh: . SilO phAro Ib Iii b(Jl trAng mill va khii bn diOOv~ hoiJt lIOO. eo d~c tnmg san day: - Ph6 hlmg ngo~i 'i) Kl3r (em-!) : 3440 (\) NIl). 2928 (\) ~tJ ), 17!0 (\) C=O cua yang trime), 1422 (\) cua soon izoxianllrat). 1228 (\) Cc) \ I 0 - Phiin lIch nguycn C% = t6 : C36H36012NG 57.90. 11%= 5.25. N% = 11.60 OJ-OJ \/2 0 - - 13 - DONG HQC CUA PHAN LING TRIME HOA yaNG ARYLMONOIZOXIANAT ChUng tei kMo sat dQng hQc phan Ung trime bOa vang cua aryimonoizoxianat C6HsNCO. p-CIC6H4NCO. m-ClC6H4NCO va 3 m -CH3C6H4NCO v6i bazO' 1a. mu6i NaCN vii chell XTCP 1a. Aliquat 336 trong dung mei axelonilril trong khoang nhi~t dQ tlI 17°C dim 430C [2]. )( , ~ NCOIOX NaCN. 5X . ,~ CN 07 N/'. Allq..! 336 ~m~ Cr th&i di&m , y. ~ twa du 50m1l d "3 CH ~ J8J ~ ~ l8J t = O. [aryimonoizoxianat] °= t = t. [arylmonoizoxianath = a - 3x a ./ 'N b ~o 0 X )< a : n6ng dQ ban dAu cua arylmonoizoxianal x : n6ng dQ cua izoxianurat t1J.Othanh PhU'O'Ilg trinh dQng hQc b~c 2 : 1 3(a - 3x) = koo't + ~ 3a D6 theo doi v~n t6c phan Ung. chUng lei sir d\lllg phU'O'Ilgpilap dp1h 1U'Q'ngnhom NCO can 1~ tll'ng th&i di~m (t) [16]. K~t qua lhgc nghi~m kill dQ chuy~n hoa phan (mg d~t 70-80% cho thely. dQng hQc cUa phan ii'ng lrime hoa vong cac aryimonoizoxianal v&i mu6i NaCN va. chell XTCP Aliquat 336 thuQc lo~ phuO'Dg lrinh b~c 2 theo n6ng d{> cUa monome. ChUng Wi Slr d\lIlg phep giai Uch h6i quy va. phllO'ng pMp binh phllO'Dg t6i lhi6u ap d\mg cho phuO'ng trinh hbi quy tuy~n tinh d6 sur ra cac hAng s6 v*n t6c k. cac thOng s6 ho~t hoa 6J{: va. 6.S:::. trt s6 p cua Hammett va. khoang tin c~y tUO'DgUng ; va. kern theo do co cho tr! s6 cua h~ s6 tllO'ng quaD r 116bi~l v~ muc dQ tuyim tinh cua cac di~m dang quail sat [5]. - 3.1 - K6tqua 14 - : 3.1.1 - C6HSNCO )}ac su§.t BANG 3 : Hftng +u6i v&i . s6 v~n t6c k. khoang tin. c{ty KTC(k) A .,. !\ P = 0.95. h() so ;.tro'ng quaD r. c-rc thOng so ho?-t hoa illl- va uS-. khoimg = 0.95 cua tin c~y KTC(Lili-) va KTC(/;;,S-) v&iP vong C6H5NCO thee nhi~t QQ. I i I i 290 T( oK) I 311 1.53 1.77 0.13 0.37 0.49 0.998 0.995 0.997 iI KTC(k).1~3moH.s-l r i 0.998 316 306.5 0.64 k.lO+ 3mo}-l.s-l pMn \rng trime boa . 2.39 f 6H~ :t KTC(LJt- ) I I i kcal 8.5 ~ 1.6 .mol-l , + I/;;,s -:t KTC(/;;,S :t) calX~ mol-l II -43.86:' r 5.10 0.998 3.1.2 - p- C1C6H4NCO BANG 4 : HfLngs6 v~n tbc k. khoang tin c~y KTC(k) ubi v&i xac . f + ., va suii.~ P = 0.95. M so ttro'ng quan r. cae thOng so ho~t hOa 6H.65:'. khoang tin e~y KTC (Lili~) va KTC (/;;,S~) v&i P = 0.95 eua puan trag trime hoa vong p- ClC6H4NCO thee nhi~t u{> i i recK) iI k.1O+3mo1-l.s-1 I I , i KTC(k).lOt3moH.s-l , I r , :, I ,i 0.26 0.996 311 I : I I I 0.40 , I 0.994 I I I Lili~! KTC(L6H~) kca1.mo1-l + ... 6s -:t KTC(/;;,S '"') cal.Wl .mol-l r ! i 5.5.! 1.0 j I II ! 316 I 1.~ I I I I 307 1.17' I I I I 293 -53.20::' 0.998 3.20 0.89 0.995 II I I 1.48 0.997 - - 15 3.1.3 - m-C1C6H4NCO BANG5 : HAng sO v~n tOe k, khoang tin e~y KTC(k) ubi v6i xae suilt P L,S=, = 0,95, h~ sO tU'O'llg quan r, cae thong sO ho~t h6a Lili.! va khoang tin c~y KTC (Lili-!.) va KTC (L,S!) = v&i P 0,95 cua phan (mg trime bOa yang ')"11.-ClC6H4NCO thee nhi~t at) BANG 5 T(OK) 293 307 T I 311 316 I k.lO+ 3moH.s-l 1.51 2.45 2,29 2.88 I KTC(k) .10+3mol-l.s-l r 0.24 0.992 0.34 0.53 0.993 0,998 0.65 0.990 I Lili! KTC(Lili-!. ) 1: kcal.moH 4,5.! 1.0 L,s !:t KTC(Lili 1: ) ea1.K-l.mol-l r -56.rn : 3,20 0.997 3.1.4 - m-CH3C£fi4NCO Rieng uOi v6i m-tolylizoxianat, chUng toi chi khilO sat hAng so v~n tOe k & 38°C va eo k~t qua sau day k.1O+3morl.s-1: 1.62 KTC(k).10+3.mol-l.s.1: 1.35 r :0,993 BANG 6 : Cae trl sO thOng sO ho~t bOa. khoang tin c~y tren pMp tinh dOi v&i xae xuilt P = 0,95 va h~ sO tU'O'ng quan r cua phan (mg trime bOa yang tily thee tUng arylmonoizoxianat. - - 16 BANG 6 i ' ~ I I ~y~ono- ,... ~Q}aanat - bOa II boat ThOng s6 . I ,+ II DB- . + KTC(DB-) I + I6s - + I It I ' -+ II 1.6 I I I I I I ;I II 5.5 -+ 1.0 ! i I : iI I -43.86 !. 5.10 ' m-ClC6H4NCO , I I KTC( 6S -) caLK-I.mol-l I IiI I ,+ I , I 8.5 kcaLmol-1 I ! + I ! p-ClC6H,j'lCO C6H5NCO i ~I I i i -53.20!. 3.20 4.5 -+ 1.0 I I I I -56.08!. I 3.20 i !! I r I 0.998 [ I, I ! 0.998 j I 0.997 i 3.2 - Kbio I!t bi~u 'Cmg4i~n tU-cUa nhbmthb tron nhAn tham BANG7 : S1,l'thay dbi cua log k theo 0 cua Hammett i:r38°C Nh6m th~ 1 r I I X 0 Hammett m- Cl 0.373 p-Cl H 0.227 0 m- CH3 -0.069 I I I I k.IO+ 3mol-l.s-1 I log k I i 2.45 2.12 1.77 : 1.62 I I i I I -2.6108 -2.6737 -2.7520 -2.7905 Tit phlrO'ng trinh hbi quy tuyfm HIm bi~u di6n cho log k theo O. La guy ra 1.1'1sb p va h~ s6 tlrO'ngquail r i:r 38°C nhu san: p : 0.39 3.3 - BiOn~ KTC(p) : 0.08 vo-i P = 0.95 r : 0,998 : a - Tit cac k~t qua th1,l'Cnghi$m. ta co th~ th~y dmg pMn ftng trime hOa vang arylmonoizoxianat trong di~\1 ki~n XTCP nhu dii mo tA cling thee dUng b?c 2 nhu trong trwng h?'P phim (mg dUQ'c th\rc hi~n trong di~u ki{m dbng tuemg. b - Hfmg s6 k ho~c kdo tinh thee phiill \rng b~c 2 co trj s6 khi cb dinti cho mbi nhi$t d{\. Di~u mly rlit 15' tM va dua-ng bi6u p-CIC6H~CO > m-CH3CsH4NCO Di~u nay cUng c6 th~ d,! doan dU'Q'cvi v&i cac nh6m th~ cang rut di~n tu, C cua nhom N=C=O cang thiE!Udi~n tu. U"UdiU cho phan \i'ng t§.n cong than h<;ich. HO'n nua, S,! ki~n nay ding duQ'c xiic nh~n b6-i tr! s6 p duang. p= Tr! s6 0,39 tuO'ng elM nho, chi rang 6- tr<;ing thai chuy~n ti~p co s,! tang di~n tieh am trai dai ta N qua O. Nhu v~y dQ nh~y cua phan \i'ng a6i v&i hi~u \i'ng cua nh6m th~ kb6ng lem l~m. d - Cac trj sb ll.y:!: tang din thee thfr t'! : m-ClQ)H4NCO < p-CJC6H4NCO < C6HSNCO . A .. + va tq so wS- am co tIi tuy{;t d6i pam dan thee thu tv m-ClCeH4NCO > p-CIC6H4NCO > Q;HsNCO Th~ t'! nay ph\l h - Xem thêm -