Diazonium hp cht

T Wikipedia ting Vit

Phenyldiazonium cation hp cht Diazonium hoc diazonium mui l mt nhm cc hp cht hu c c chung nhm chc RN 2 + X - trong R c th c bt k d lng hu c nh alkyl hoc aryl v X l mt anion v c hay hu c nh mt halogen . Diazonium mui, c bit l nhng ni m R l mt nhm aryl, l trung gian quan trng trong tng hp hu c ca thuc nhum azo . [1]

Ni dung
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1 Chun b 2 Phn ng o 2,1 Displacement ca N 2 nhm o 2,2 Diazo ghp o 2,3 phn ng khc o 2,4 kim loi phc hp o 2,5 ghp phn ng 3 ng dng o 3,1 hu c tng hp o 3,2 Niche s dng 4 An ton 5 Xem thm 6 Ti liu tham kho 7 Lin kt ngoi

[ sa ] Chun b
Qu trnh hnh thnh cc hp cht diazonium c gi l "diazotation", "diazoniation", hoc "diazotization". Phn ng ny ln u tin c bo co ca Peter Griess nm 1858, ngi sau pht hin ra mt s phn ng ca lp ny mi ca cc hp cht. Phng php quan trng nht cho vic chun b ca cc mui diazonium l iu tr cc amin thm nh anilin vi acid nit . Thng thng cc acid nit c to ra ti ch (trong cng mt bnh) t nitrit natri v axit khong sn . Trong dung dch nc mui diazonium khng n nh nhit trn 5 C; cc N-+

N nhm c xu hng b mt khi N 2 (kh nit). Ngi ta c th c lp cc hp cht diazonium nh tetrafluoroborate mui, c n nh nhit phng. Thng thng, cc hp cht diazonium khng b c lp v mt ln chun b, c s dng ngay lp tc trong cc phn ng hn na. Cch tip cn ny c minh ha trong vic chun b ca mt hp cht arylsulfonyl: [2]

N thng c a thch rng mui diazonium vn cn trong cc gii php, nhng h c xu hng qua bo hoa . Cc nh khai thc b git v b thng bi mt kt tinh bt ng ca cc mui sau v n ca n. [3]

[ sa ] Phn ng
[ sa ] Lu lng ca nhm 2 N
Nhm diazo (N 2) c th c di di trong mt qu trnh gi l dediazoniation, m bn pht hnh nit N 2 v aryl carbocation mt hoc nhiu hn thng kt hp vi in t duy nht chuyn mt aryl cp tin . [4] Dediazotization thng gy ra bi halogenua . Qu trnh ny l mt hnh thc thay th vng thm i lc ht nhn phn ng, l c s ca cc phn ng Sandmeyer , cc -Bachmann Gomberg phn ng v phn ng Schiemann . Trong phng php gi l Craigso, 2-aminopyridine phn ng vi nitrit natri, acid hydrobromic v vt qu brm bromopyridine-2. [5]

Mt s phng php khc tn ti cho dediazotization:

bi gim hu c ti mt in cc bi bc x gamma t in t solvated to ra trong nc photoinduced chuyn giao in t gim bi cc cation kim loi, ph bin nht l mt cuprous mui. anion gy ra dediazoniation: a counterion nh i-t cho chuyn in t n cc cation diazonium hnh thnh aryl cp tin v mt it cp tin dung mi gy ra dediazoniation vi dung mi phc v nh l nh ti tr in t

[ sa ] Diazo ghp

Mt phn ng quan trng ca mui diazonium thm l azo ghp . Trong qu trnh ny, cc hp cht diazonium arenes cuc tn cng in t phong ph nh anilines v ng thi phenol vi bn pht hnh ca proton. Qu trnh ny l mt v d v thay th thm lc in t : Arn 2 + + Ar'H Arn 2 Ar '+ H + Kt qu l cc hp cht azo thng thuc nhum hu ch, v trong thc t c gi l thuc nhum azo . Nhng mu sc su sc ca thuc nhum phn nh m rng ca h lin hp .

[ sa ] Cc phn ng khc

Trong Meerwein arylation mui cng b phn hy v cc d lng aryl phn ng vi mt thiu anken in t trong mt phn ng ngoi Trong tng hp triazine Bamberger v cc -Stoermer tng hp Widman mt mui diazonium phn ng nh l mt electrophil thng qua nguyn t nit b u cui ca mnh vi mt lin kt i kch hot. Thy phn ca mui diazonium sn lng ru Gim vi acid hypophosphorous thay th nit bng hydro, cho php amin (v, gin tip, cc nhm nitro) phi c loi b Trong phn ng Heck-Matsuda cc cp v chng mui vi mt anken.

[ sa ] kim loi phc hp

Diazonium cation tng t nh NO + v do hnh thnh cc phc vi nhiu kim loi trung tm, c bit l trong ha hc organometallic . Cc hp cht ny thng c chun b bng phn ng trc tip ca cc phc kim loi thp Valent vi mui diazonium. Minh ha phc l [Fe (CO) 2 (PPH 3) 2 (N 2 Ph)] + v cc chiral-at-kim loi phc tp Fe (CO) (NO) (PPH 3) (N 2 Ph). [6]

[ sa ] phn ng ghp
Trong mt ng dng tim nng trong cng ngh nano , diazonium cc mui 4chlorobenzenediazonium tetrafluoroborate rt hiu qu functionalizes ng nano n vch . [7] ty t bo cht cc ng nano, chng c trn ln vi mt cht lng ion trong mt ci v chy . Cc mui diazonium c thm vo cng vi kali cacbonat , v sau khi nghin hn hp nhit phng b mt ca ng nano c bao ph vi cc nhm chlorophenyl vi mt hiu qu ca 1 trong 44 nguyn t carbon. Nhng b sung subsituents ngn nga cc ng hnh thnh b thn mt do ln lc lng gn kt gia chng, m l mt vn nh k trong cng ngh ng nano. N cng c th functionalize tm wafer silicon vi mui diazonium to thnh mt aryl n lp. Trong mt nghin cu, cc b mt silicon c ra sch bng hydro florua amoni li n bao ph bng silicon-hydro tri phiu (hydride th ng). [8] Cc phn ng ca b mt vi dung dch mui diazonium trong acetonitrile trong 2 gi trong bng ti l mt t pht qu trnh thng qua mt gc t do c ch : [9]

Cho n nay ghp ca cc mui diazonium v kim loi c hon thnh vo st , coban , niken , bch kim , paladi , km , ng v vng b mt. Ngoi ra ghp vo mt vin kim cng c ghi nhn. [10] Mt iu th v l vn nng ln v tr thc t trn nhm aryl vo mt. Mt trong silico hc [11] cho thy rng trong thi gian 4 yu t t titan ng cc nng lng lin kt gim t tri sang phi v s lng-in t tng d. Cc kim loi bn tri ca st c t nghing v pha hoc cn h trn b mt kim loi thin carbon tri phiu pi hnh thnh v nhng ngi trn bn phi ca st c t mt v tr thng ng, thin kim loi carbon kt sigma hnh thnh. iu ny cng gii thch ti sao diazonium mui ghp vy, n nay c th vi nhng kim loi trn bn phi ca st trong bng tun hon .

[ sa ] ng dng
Vic s dng u tin ca cc mui diazonium l sn xut nc nhanh nhum vi bng cch ngm vi trong dung dch nc ca cc hp cht diazonium, theo sau bng cch ngm trong dung dch ca cc b ghp (cc vng in t giu c tri qua s thay th lc in t). Vic s dng hin nay ch yu vn l trong ngnh cng nghip nhum. [12]

[ sa ] hu c tng hp
tho lun trn theo phn ng, diazonium l cc hp cht hu ch trong vic chun b thay th thm t cc hp cht anilines. Nh Fluorobenzene v d l do s phn hy nhit ca phenyldiazonium cc tetrafluoroborate: [13] Bnh PHN 2 BF 4 PhF + BF 3 + N 2

[ sa ] Niche s dng
mui Diazonium l nh sng nhy cm v ph v di gn tia cc tm hoc nh sng tm. ti sn ny dn n s dng trong sinh sn ti liu. Trong bi ny, qu trnh hay b phim c ph mt mui diazonium. Sau khi tip xc lin h theo nh sng, cc diazo cn d c chuyn i thnh mt n nh thuc nhum azo vi mt dung dch nc ca cc b ghp. Mt qu trnh ph bin hn s dng mt giy trng diazo, ghp v axit c ch s ghp, sau khi tip xc vi hnh nh c pht trin bi mt hn hp hi ca amoniac v nc m cc lc lng khp ni.

[ sa ] An ton

Diazonium mui thng nguy him bng n, v t vong v thng tch c bo co. Trong thc t, peclorat diazonium aryl, chng hn nh perclorat nitrobenzenediazonium l tng i n nh, c s dng trong vic xng cht n.

[ sa ] Xem thm

Diazo Benzenediazonium clorua

[ sa ] Tham kho
1. ^ Ha hc ca cc nhm v Diazo Diazonium: Phn 1. S. Patai, Ed. Wiley-Blackwell 1978. ISBN 0471994928 . Ha hc ca cc nhm Diazonium v Diazo: Phn 2. S. Patai, Ed. Wiley-Blackwell 1978. ISBN 0471994936 . 2. ^ RV Hoffman (1990), "m-Trifluoromethylbenzenesulfonyl Chloride" , Org. Synth. ; Sb. Vol:. 7 508 3. ^ "Anh CRHF Bo co s c - bo Diazonium mui nguyn nhn t vong" . Truy cp 13 thng 5 nm 2010. 4. ^ Carlo Galli (1988). "Cp tin phn ng ca cc ion arenediazonium: Mt mc nhp d dng vo cc ha hc ca cc gc aryl". Chem. Rev 88 (5): 765. doi : 10.1021/cr00087a004 . 5. ^ Lyman Craig C. (1934). "Mt nghin cu v cc chun b ca Alpha-Pyridyl Halogenua t Alpha-Aminopyridine bi cc phn ng Diazo". J. Am. Chem. Sc. 56 (1): 231-232. doi : 10.1021/ja01316a072 . 6. ^ Sutton, D., "Hp cht Diazo Organometallic", Chem. Linh mc nm 1993, khi lng 93, 905-1022. doi : 10.1021/cr00019a008 7. ^ Green Ha cht Functionalization ca Walled Carbon ng nano-n trong cht lng ion B. Gi Katherine, Jared L. Hudson, v James M. Tour J. Am. Chem. Sc. ; nm 2005; 127 (42) Trang 14867-14870. doi : 10.1021/ja053998c 8. ^ Michael P. Stewart, Maya Francisco, Dmitry Kosynkin V., Shawn M. Dirk, Joshua J. Stapleton, Christine L. McGuiness, Allara L. David, v James Tour M. (2004). "Trc tip ghp cng ha tr ca lin hp phn t vo Si, GaAs, v Pd b mt t Aryldiazonium mui". J. Am. Chem. Soc. 126 (1): 370. doi : 10.1021/ja0383120 . PMID 14709104 . 9. ^ chui phn ng: silicon b mt phn ng vi hydro florua amoni to ra hirua lp. in t An c chuyn t b mt silicon vi mui diazonium trong mt mch m tim nng gim li mt silicon cation cp tin v diazonium mt cn. Trong bc tip theo mt proton v mt phn t nit b trc xut v hai d lng cp tin ti t hp to ra mt b mt silicon lin kt cacbon. 10. ^ SQ Lud, M. Steenackers, P. Bruno, DM Gruen, P. Feulner, JA Garrido, v M. Stutzmann (2006). "Ha cht ghp ca t lp rp n lp biphenyl trn Diamond Ultrananocrystalline". J. Am. Chem. Soc. 128 (51): 16.884. doi : 10.1021/ja0657049 . PMID 17177439 . 11. ^ De-en Giang, Bobby G. Sumpter, v i Sheng (2006). "Cu trc v kt dnh gia mt nhm aryl v kim loi b mt". J. Am. Chem. Soc. 128 (18): 6030. doi : 10.1021/ja061439f . PMID 16669660 .

12. ^ Klaus i, Peter Mischke, Wolfgang Rieper, Raue Roderich, Kunde Klaus, Aloys Engel "nhum azo" trong ting Vit ca Ullmann Ha hc cng nghip, nm 2005, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a03_245 . 13. ^ lt, DT (1943), "Fluorobenzene" , Org. Synth. ; Sb. Vol. 2 295 .