Scribd Logo
Unggah

Selamat datang di Scribd!

  • Diazo Compounds

    Diunggah oleh

    marcelompassos
    14 tayangan10 halaman
    Diazo compounds and their derivatives - synthesis, reactions, mechanisms

    Hak Cipta

    © © All Rights Reserved

    Format Tersedia

    PDF atau baca online dari Scribd

    Apakah menurut Anda dokumen ini bermanfaat?

    Apakah konten ini tidak pantas?

    Laporkan Dokumen Ini
    Diazo compounds and their derivatives - synthesis, reactions, mechanisms

    Hak Cipta:

    © All Rights Reserved
    Unduh sebagai PDF atau baca online dari Scribd
    Tandai sebagai konten tidak pantas
    14 tayangan10 halaman

    Diazo Compounds

    Diunggah oleh

    marcelompassos
    Diazo compounds and their derivatives - synthesis, reactions, mechanisms

    Hak Cipta:

    © All Rights Reserved
    Unduh sebagai PDF atau baca online dari Scribd
    Tandai sebagai konten tidak pantas
    dari 10
    87 iarocoMPOcKDN: 4x9: THUR -DamYATIVES. CHAPTER -XXIV. DIAZO-COMPOUNDS AND THEIR DERIVATIVES, Ti hia already been atatod that when the amide-compounds or their salts are treated with nitrous acid in aqueous solution, thoy yield phenols; this decomposition, howover, astally takes place only on warming. If, far example, a well-cooled dilute solution of aniline hydrochloride (1 mol.) bo mixed ‘with sodium nitrite (1 mol), and hydrochloric acid (1 mol) ‘added to set free the nitrous acid, phenol is not pro ‘duced, and the solution contains a very unstable substance, called diaznlensene chloride, the formation of which may be ‘ekpressed by the equation SOHN Vy HCl + NOM = GjHyNENCI + 2110. Tr this respect, then, the anide-compounds dir fromthe fatty amines} the Itterareat once convert int aleahols by ittoan acil in the cold, wheres the former are first tran formed into diseocompotns which, usually only on wetming, decompose more or lew reedily with formation of ‘phenols (0.386) “All amido-compounds behave in this way, yielding diame sais similarly enditted to dazobensene chloride. ‘The dioaalteworo dieovered in 1860 by P. Gress they may bo assumed to bo malts of diazobensene, CHyyN:N-OF, ful its homologuos aabstances which it bas not hoon found pote to isolate in a pure state and analyse on acount of thie unstable nator. ‘The dinoaalta (anally epoken of as the diaz-composnda) way novortheleo be isolated without mach dificult, although, tet matter of fat, they ere seldom aepatted fom theit ‘1juooun solutions, partly Bocause of their explosive chaser, DIAZOCOMPOUNDS AND THEIR DRRvATIVER $7) partly because for most purposes for which they are prepared ‘this operation is quite unnecessary. Preparation —Anhydrous dizosslts may be obtained by ‘treating « woll-cooled solution of an amido-compoand in saboolute aleohol with amyl nitvite and a mineral acid, in ‘absence of any considerable quantity of wate, CHyNH,HO! + C,H,.0.N0 O,HyNNCL + C,H, OH + 10. Diacobensene sulphate, CiHeN:N-SO,k, for example, is pre rod by dissolving aniline (13 parts) in algolate aleohol (i0 pare), ssdding concentrated sulphuric. act (20 parts), tnd alter eoling in a freezing mixture, lowly running in pure amyl altte (20 sans); after 10-15 minutes diaabonzene nulphate separates te ‘egyeials, which ate washed with alobol and ether, ant tefed in ‘the air at ordinary temperatares Diasobensene chore and diacobensene nitrate may be obtained similar manner, employing. alcoholic solutions. of hydrogen ‘edlovite and of nitric acid inthe place of sulphuric acja, Diazobensens nitrite, CH-N-N-NO,, may also be conveniently Sbolatod ax follows: Aniline nitrate tstspented ina soll quantity (of water, and the fiquid saturated with aittons acid (generated from As,0, and HINO,), when the erjatals gradually dissolve with formation of diazobensene nfteate; on the addition of alcool and ether, this salt separates in colourless needles. Special precew ‘ions are to he observed in preparing this ubstance, as; when ity, itis highly explosive, although it may be haudled with safety kept moist. Aquoous solutions of the dinosalts are prepared by dis- the amido-compoand in an aqueous tuineral acid, and ‘ding the theoretical quantity of a solotion of sodium nitite, after firat cooling to 0° (see above, also p. 373). Propertics—The diazo-salts aro colourless, erystalline com- ‘Pounds, vory readily soluble in water; in tho dry state they fare more oF less explosive, and should be handled only with the grontest caution, They are of immense value in ayntheti- eal chemistry and in the preparation of dyes, as they mndergo ‘© number of remarkable reactions, of which the follpwing are ‘some of the mote important 313 piazo-CoMpousps AND THxIR DERIVATIVES, ‘When wat in agunoslton Sy dspone pil vil mast of afogon a fran poncl (386), GigNNNO, + HO » Gl,OH +N, + HNO, OCH) NNCL + M0 —GHACH).O# Ny + CL ace fa en biel eh arog aloha they yi hydnvaions ort ofthe dhol bing one lig, GHyNINCI 4 C,OH = GH, + Ny + HCL 4 C1,CHO, Thee two rocinns afd 2 meant of cinining phase to hydoebons fom andoconprnds Se Speuads bare rey miosis ay whee tenet wth eprom all; or etompl olin WrdasSboone chloe bo warned wih exrom ead Senet ted and shnsboane afte In thi wae te diavas combine, with Eh eros chide Tinet a inamolite owas sddtve compound, wich eet at Nghe. tenpontrey capri thinnest the mason sonnel Coy Ne + Coy 1h intend of he clad, exproas oie or ens snd he omploe,bomotsnane or indobonene inode, GHLNNBeCugbe, = Cle + Ny + Cody NNCI, CuCl, = GH,Cl + whereas by using cuprous eyanide, a cyanide or nitrile is formed, Gly Ny CN, Cuy(CN), = GjHyCN + N, + Ca,(CN), “adie Copa Phat] Case Tn this latter reaction a mixture of eupric sulphate and potassium cyanide is gonerally used instead of the previously prepared cuprous eyanide. By meant of this very important reaction, which was imovered by Sandmeyor in 1884, itis possible to displace the DiAZO-COMPOUNDS AND THR DERIvanIvES, 873, NH,~ group in smidocompounds by Cl, Be, 1, CN, and indirectly by COOH (by the hydrolysis of the CN group) and indeed by othor atoms or groups; a8, moreover the yield is gonerlly. good, Sendmeyer's reaction is of great practical value, The amido:compounds being readily obtainable from the nitrocompounds, and the latter from the hydrocarbons, this rmothod alfords © means of preparing halogen, eyanogen, and thor derivatives indirectly from the hydroearBons Gatterma has alow that tho degomposition of the dina compass in, in many eam Yet brought oat by reatng he cold mltion of th dsersal wth npper power (prepared hy he Seti of sine dant om a mlation of ceppe sulpe). Monocle tenzen, fr example, ie enily oltaoel trom tine by te fellowing proces: Aniline grou) ie diolve i hydvochlore fei (00 rats) ant water (10 gran}, th solution well cole With ic, and inated ang gray concentrate agen Relation a odin aitite (gree) The alin of taaobencene Chloride thaw obtinel i graally mixel with copper powder fram), wher tren is valved tn ehlorobeugee protec action Ung complete in about half an hur Ee chlorobenzene then pared by dst in aenm ant fetinaton Tn preparing eytotenne, GiiyC, from none aniline wl ten dastive, the wtion mined with putasrum cea, and Shen cope power sd The dinzocompouncs alto serve for the preparstion of an portant clas of compouns Known as the ydrsines, tho substances being obtained by reducing tho dio compounds, tmvally with stannous chloride and hyrvelovie ai RAN-NCI + 4H = RNIENH,HOL Dacia Hira yn Constitution of Diasrcomponnds—Thatd ave the cnstion exprsse by the formule Gg (where R= Cl, Bs, I, NOy HSOy &e) is shown by the following considerations, Ow reduction they are converted into phenylhydrazine, C,HyNH-NH, (the constitution of which is knowa, p. 376), a fact which shows that the tivo nitrogon atoms are united together, and that one of them (2) $74 DIAZO-COMPOUNDS AND THRTR DERIVATIVES, 4s combined with the benzene nucleus, Diazobanzene ghloride interacts readily with dimethylaniline, giving dimethylamido- azobenzene (p. 376), GHLNNC + OHy-N(CH), = C(Hy NN-CH-N(CH,)-+ HCI, snd this sublans, on redution; ysl aitine and dimethyl pphenylenediamine (p. 378), Gg NN-CH-N(CH), + 4H = CH NH, + NH,-CH N(CH.) ‘Theto changes ean only be explained on the assumption that the acid radi is attached to the eaitrogen atom, ax in tho ‘above formula, because if it were united to the other nitrogen atom @) asin the formula GlyNCIN, for example, eoeh products eotld uot be obtained. ree diazobenzene is very unstable, and has not bean obtained in ‘a pore state, bubit probaly has the constitution C,H-N:N.O Diazoamido- and Amidoaco-eompounte. Although some of the more characteristic reactions of Giazo-compounds have already beon mentioned, there are numerous other changes of great interest and of great com ‘mercial importance which these substances undergo, ‘When, for example, diazobenzono chloride is treated with ‘aniline, a reaction takes place similar to that whiel oceurs when aniline is treated with benzoyl cliloride (p. 420), and diazoamidobonzene is formed, Gy NNCI + NH, CH, = CH NNEC H, + HCL GjHyCOCl + NHYC\H, = CH,.CO.NH.G,H, + IC ‘Benny nldtenne Bennie As, moreover, other diszo-compounds and other amido compomnds interact in a similar manner, numerous diazoamide- compounds may be obtainod. Diazoamidobenzens, C,H, N:N-NH.GH, may be doy DrAZOOOMPOUNDS AND THEIR DERIVATIVES, $75 “wetibed as « typical compounsl of this class; itis conveniently Prepared by possing nitrous fumes into an aleoholie solution f suiline, the diazobenzene nitrite, which in probably fist Produced, interacting with excess of aniling GH,-NN-NO, + C,HyNH, H,NN-NH-G,I, + HNO, Diszoumidobonzene erystallises in brilliant yellow needles, fand is sparingly soluble in water, but readily in alvohol and ‘ether; it dovs not form salts with acide Amidoazobenzone, C,1,N:N.C,H,NH, is formed when liazoumidobenzene js warmed with a small quantity of aniline Ihydrochloride at 407, intrsmoleculer change taking place, Oop NN-NH.CH = Oy NENG, NHL, Tho coarse ofthis remarkable reaction, which is a general one, god shown by all diasoumite-compounds, may. ponstly explained by assuring that tho aniline hydvochlorite het decor poses tho diazoumidobensene, yicling diazobangene chevile sailing thus QHLNIN-NH-GH, + CllyNHy HCL = C,-NNCI+ 20,3 ‘Tho diazobenzene chloride then interacts with exctss of eniline uch a way that the diazo-groupdlaplaces hydrogen of the nacioce from the para position to the uinilorgroey, CHEN NCI + 20411, NH= C,H -N-N.C\H, NT, + C\lpNHy HCL, ‘The chang is therfore, theoretially continoas, the regenerated allie hydrochloride being able to convert farther quanti at ‘the diazoamidotenzene into the amidoazo-compound, Amidossobenaete may ako be prepared by uitrating Gzobenzene (p. 378), and then reducing the paitnane Denzone, CQHN:N-C,HyNOs, which is produced. with smmoninra sulphide, a seties of reactions analogous #0 those Which ocsit in the formstion of aniline from bengene, and which prove the constitation of amidoazobenzene, Anmidoazobenzene crystallines from alcohol in brilianb erango-red plates, and melts at 125°5 ite salts are intensely coloured, the hydrochloride, CyH,-N:N.C,H,NH, HCl, for example, forms beautiful stoo-blue needles, ahd used to some 876 vrazo-compouspe axD THEI pxnivativEs, into the market under the name of ‘aniline yellow’ Aye (p. 524). Other auidoazo-compoanss may be obtained directly by treating ‘tertiary akylanilines(p. 364) with diago-salts;dimethylaniling, for example, internets with diszobenzene cllorsl, yielding dimethyl. aidoazobenzene, CHE NENCI + CQHyN(CH,) = Cylly NN-Cl, N(CH, HCl, no intermediate dinzaamido-compound being formet, because imethylanitine does aot contain an NH

    Anda mungkin juga menyukai