um m zm m & zm m m Walter Behert Kmx A dissertation submitted In partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry in %he Graduate College of the State University of Iowa August I950 ProQuest Number: 10666175 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10666175 Published by ProQuest LLC (2017). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346 ' T v ^ o W A r 0- 0 0 . &- I wish t© express Ey appreciation i© Professor MLph I*. Sbriner for Ms enthusiastic guidance throughout this study. I als© wish to express ®y appreciation to the faculty of the organic chemistry division of the State University ©f Iowa* for ®a©y helpfnl suggestions* r os X U ii £m> Charter %tx& i wm m m m *?$. % ♦ * * mmowmh m i i j 3 H i mnmmtm vwssaam * * . . . . . . . . . . . . . 9 A, Btc&ies «a- 1,3~3iph6isyl~2~heE£opyryIi^ Salts. . . . 9 B. S tales© a 1,3* 4V£riph©isyl^2-ben2Gpyrylim Salts . . 14 j C* Jgesevtega* Siraetnres of S^Bengopyrylim Salts. * , *2 15, Absorption Spectra of 2~Benz©pyryliPm Salts and Helatsd Gomponnds. . . . . . . . . . . . . . . . 29 Mwmmmm I? ..............................................................................4i acid . . . . . i &I H©©©phihaXie amfc^&rl&e . . . . . . . . . . . . . . . . 42 3-Phai^llsecomarla . . i * 42 1 # 3-Blphenyl-2~beasopyryl lam perchlorate. . . . . . . . 43 1# 3-Blph©Byl-2-Mns©pyrylitiEi chloride . . . . . . . . . 44 1 # 3~MpMnyl~2-ben2©pyrylinm bromide . . . . . . . . * 44 1* 3*Slph©nyl^2^'b©nzGpjr3rlinffi ferriehlorid©. . . . . ( . 45 1,3~£iphesyl~2~bensGpyryXinm ferri’broml&e . * . . . r'. .4 5 $ Ozonolysis of 1 3~d iphenyl-*2~'ben zopyry1 in® perchlorate . . . . 4 6 Bensalphthallde . . . . . . 46 2,3^BiphenyIiEd©ne ........................ 4f 2Jfc3*Btphei^liad^©. . ..... 4 * * * . . . . . . . . . . 48 - (Q-Beiixoylphjenyl 5-ac©topfcenone and conversion to 1* 3^Iph®nyi~2~hen£opprylisaa perchlorate. . . . . . . 49 2* 3-'%Gsy-2#3-diphenylinda»on© * . . . 5© 3* 4^Biphes^liscconcJarlR . . . . . . . . . . . . . . . . 5© 3f ^Trlp3seajrl-2*-heiis:op7r^lli2Ei perchlorate . . . . . . 5© OiKWJolysts of 1.3*4~triphenyl~2~)^n£opyrylinja perchlorate . . . . . . . . . . . . . . . . . . . . .5 1 l~Phenyl~3* A-dti-t p* ~ni tr©phenyl )-*2-henKop^ry linan perchlorate • • . • . • . . * • . . . . . • • . . • • 5 2 Osonolysis ©f l-phenyl~3. p* -ni trophenyl )~2~ beazopyrylicm perchlorate * . 4 . . . . . . . . . . . 53 Phenylphthalide . . ..................................... 54 ill Chanter £a23. o-aiieMoyi benzene. ....................5 ^ (p'-AiBlnobenzoyl )-e-benzojrl benzene. .............55 (p*-Hitrobenzoyl)*o*-benzeyl benzene. . . . . . . . . 56 Measurement of absorption speotra . . . . . . . . . 56 V SQNNAST .................... 62 n ttsuomtsm, . 63 m aiosa«?sr , .................................................................65 iv X Gh&pter I Most organic! compounds are characterized By the fact that the carbon atoms are covalently linked to other atoms* Relatively few types of compounds possess physical md chemical properties indicating Ionic structures in which the earhoa atom lo present as a positive earbenlum ion or a negative Cartmnlon* £w© eltueturee possessing carbonim lone are the trlarylmethyl derivatives (1) and hemsopyryllnai salts (II)* fhese formulas represent only one of several contributing resonance alruc~ turee. 0 I IE A survey of the literature revealed that only two definite examples of leobemaopyyyltum salts (III) have been prepared. Structure (111) is isomeric with (II) and again the formula drawn is only one of several resonance contributors. Because it represents an unusual and Interesting type of carbonic® salt* It was of interest to devise methods for the synthesis of isobenzopyry 1 ium salts and to study their properties. Cl On. 3 Ofe&pter II nm&itiCAi m wmmmwM* In 1909 Etcher end I’elser (I) prepared th© dibonsopyxyllum sell (?) ftm dibease~Oh pyroae (I?)* Ft Uv 3 2 3 Z Inspection of the structure of formula ? shows that it may be regarded as a bemaepyyyliuja sail (rings A and B) or as an isobeasopyryl lum salt (rings € and ®). Only two examples of mfuestioaable isobensopyryllm salt struc­ ture have been described. the parent tsobeazopyryUu® salt (VII) was obtained V HttJttt and Eobinsoa (2) as the result of the action of lead tetraacetate on tr^as-l T2-hydriadanedlol (VI)* ^he intermediates were not Isolated hut the solution containing them yielded the ferrichloride after addition of ferrio ohlorlde and hydrogen chloride. CHO \ f* CH-CH i H ‘Eh© structure shown was based m the faet that mam.&a converted It to ieoquinoliae. Shriner and Johns tea (3) also prepared a salt of definite ise~ benzopyrjrllum nature hjr the action of phenylm&gne slum bromide on iso** couei&ria* ONfyoh Ct H$flAg8>- NH+O -y m 5 $he addition compound was decomposed hy am ammonium chloride solution, and the carhimol (II) yielded the perchlorate (X) upon treatment with perchloric ad d. It may he seen that these two preparations outline two distinc­ tively different method© for the preparation of Isoheaisopyryliu® salts. Both methods however* precede through the same type of heml^aeetal, or homi-ketal, which may also he considered as a oarhl&ol. Im the ease of j|& or $r| substituted phenyli aohenjsopyrylium salts it would he espeeted that they might he prepared from either the corresponding lactone* with phonyImagneslw hremi&e, or the diketone hgr the simple addition of strong acid. with i*3^diphonyi*2^hens#p2rxylium perchlorate (XII) these two procedures may he outlined as follows?