PREPARATION OF MERGURATED TOLYL-FURFURANES BY HARRY FRANCIS WATSON THESIS FOR THE DEGRE E O F B AGH ELOR OF SCIENCE IN CHEMISTRY GOELEGE OF LIBERAL ARTS AND SCIENCES UNIVERSITY OF ILLINOIS 1922 /922 VV333 UNIVERSITY OF ILLINOIS Mfty_ 3 ^ 192^ THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Harry Francia Watson ENTITLED ® IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF in Chemistry Approved bi'.A-k HEAD OF DEPARTMENT OF 600254 Digitized by the Internet Archive in 2016 https://archive.org/details/preparationofmerOOwats AcknowledR-ement The preparation of the raer curated allyl cresols v;as undertaken at the suggestion of Dr. Roger Adams. I wish to express my thanks for the kindly help and suggestions of Dr. Adams hy means of which the work ?;as conducted. - fi I ^ » : A - j ' — r Wvv , ^' rP'i’i'.'j A- Vi-n^ v-n '.'> 'iffi .w i^f' ♦ -• * . . ‘ ‘^Sai •»^ >: i ,. ■' \l ' io, f'^- ■ ■- ^ '■‘ ’ ,i : \ ^ I ‘ > fitf, - V* :> • ' -i -i I'*.. I' ^ • * w* * .* ‘L A I'iV^rr t The Preparation of Llercurat e d Tolyl furfuranes* by H. k'/atson Table of Contents Page History, Bibliography and Theoretical Considerations of the Organic Ilercury Compounds 1-4 Experimental 5-13 Conclusion 14 History and Biblio^ 2 :raph .7 of the 0r:5:anic Hercury Oompounds* The first organic mercary compound v/as obtained by A.u'.Eofman in 1845 from the interaction of mercuric chloride and aniline. In 1850 I’ranlcland obtained GH^Hgl o by the reaction between ethyl iodide and merciu-y. In 1855 Zinn discovered the mercurated allyl compounds, which he made by the reaction between allyl iodide and mercury; giving GH 2 =GK-GH Kgl* Tlie general method for the prep- aration of organic mercury compounds was discovered by Franhland in 1865: the sodium amalgam is treated v/ith allcyl iodide in ethyl acetate solution; the di alkyl mercuiy compound is formed as shov/n 2GH I HgSITa 5 21IaI GHrz-Hg-GHr. . In 1880 Zutscheroff made the first o o systematic study of the action of mercury salts on allyl- ene and aceytlene; however the stru.cture of the triple bond mercurated compounds is still in doubt. It was tiiDUght the work of Bilboni and Paolini that the mercury derivatives of the allyl phenyl ethers v;ere first isol- ated and studied. Bibliography The references consulted in the historical and theo- retical discussion are ’.Thitman’s Organic Compounds of Hercury, pp. ( 15-40) ,( 284-286) ; Bilboni and Paolini, Berichte- - 2 - £994-2998, Berich1:e 3575. Ivlanchot:- Annelen der Ghemie 420 , pp. 170-176; 421 , 366-569. Theoretical Discussion. A general" method for the preparation of organic mercury compounds from an unsaturated aliphatic is the treatment of the compound v.ith a mercuric salt in aqueous or alcoholic solution^ The general reaction is an addition of Hg and OH to the double bond in aqueous and an Hg and OCH^ in k) methyl alcohol solution. The addition compounds of-. ethyl- ene have been the most studied, the general reaction being: CHgsGHg 2HgXg HgO XHg-GHg-CHg-OH 2CH^=GH^ SHgXg HgO XHg-GHg-GHg-OzGHg-CHgEgX HX The proof of the stucture of the mer curated ethylene compounds rests upon the ease Vidth which ethyl alcohol may be formed from the first compound, and di-iododiethyl ether from the second. Opposed to this belief in the stiucture given is the molecular formula BG^H^HgOHgX^ and GgH^HgfOH). Ilanchot inclines to the molecular structure, basing his conclusion on the esse with v/hich the compounds are broken dovm with dilute HGl, giving OgH^ quantitatively when an alcohol would be the natural expectation if an addition compound is formed. f i i'U :l> -.')i •i ■•'a / ' if t *« . ie i ^1 ... . ..• « » k. 'V I f ■. (. l\ V 0 ' 4 ■ ■ . ■ ., . ' '.< C «'l*l The mercury compounds of the allyl phenyl ethers formed from mercuric salts are thought by ivlanchot to give t\vo compounds, either isomeric or polymers (Annalen 421 , 316-520). luanchot inclines to;vard the belief of a rnolecul or compound and not an addition, basing his belief on the ease of hydrolysis with HOI to give the original allyl phenyl ether and HgOl. He attempts no explanation of the inertness of the mercury toward HaOH or vHiitman considers that it is probable that one of the compounds maybe molecular, the other an addition product. Hr. Adams suggested that the cresols v/ould probably form mer curated furfuranes similar to those formed from the phenols. The reaction is probably as shovm: ITI4OH Purpose of the . experimental iiYorIc OH OH Cl GHgsxGH-Ghg HgGl GH^zGH-GHgHgGl ■5 0 GH£-GH-GHHgGl f,' i-KL ':VV n • •’'f ' ., nW \s ' i. V' ■ I #l*t\ - '. ^*A ,. 0 IV'i. ^ i iljL'jr '»*' ^ , . *• I& '1 ,^» • 1 -; '• 'U^.l 1 * ' . %' on . ,',,,•■ fn '■'>^^. , ,n',. Ui b^jj' e>*t4" \.,, ,'i, ^ ■ > i ♦ *, i i i ^:iS, ■" ' : ,*t : JfiV ^■j. ’A) . % 4 . , " • ! y;*. f.f- j r , , .-'f : i.^ *• -^ . . t.S'W/ V .V ,'i\ ' i 5 ■iVi ■ J'A ''• ► , :i. j I V ■y .:>, . ^ gr.rttj W 5 B 52 : ^ Jh^t -^%i' - 4 ~ CK^ GH.. c o GH GH-GH HgGl GHp-GH-GH HgGl GH„ o GKg-GH-GE EgCl 0 The general reaction with compoimds of the type H-GE^sCEg is EGEg- GE£ R-GSg-GSg EGl G1 EgGl OE EgGl The research was undertaken in order to prepare mercurated furfuranes from the cresois similarly to those prepared from the phenols. -5- Zxperimental i/Vork Allyl bromide was prepared according to t2ie method given in "Organic Chemical Heagents" vol. I. The allyl para-cresol ether was prepared accoring to method given by L. Glaisen( Annalen der Ghemie, 401 , 21-119. The distilled ether was rearranged to allyl papa cresol according to the method of Glaisen^as cited- The material v/as distilled at 20 mm. pressure, dissolved in lO^b haOH, the alheline solution washed twice with petroleum ether, the cresol precipitated with HGl, and extracted v/ith petroletima ether, and the petroleum ether driven off. Yield of purified material 64 grams from 100 grams of para cresol. Yield 46,'o. Ireparation of the Tolyl Mercurated IPurfurane . I’ive grams of the l-methyl-S-allyl-4-hydroxybenzene was added to 9.2 grams of HgGl^ dissolved in 250 c.c. of water. Hapid mechanical agitation was used for four hours and then stood over night. Yield 10.1 grams of dry gran- ular material. The material was crystalized from hot alcohol three times, clean crystals were obtained. Yield of crystals 6 grams. M.l. 99.0^-99.5^^. mother liquor gave no syrup- like bodies. A second lot was similarly prepared; yield 6.6 grams II. 1 . 99 * 0 ^. 09 , 50 ^ I' • '( i! .i*: ' ’ iwfcljpfallijiii * " a ' 1 Ff '1 ■ iS \ ' (-KkV^'Lli . ■' i :. toli- CC 4 ,, ' ! 'i V 4 ’* 1 ‘ vX i . : ', (». « 'f -o- The first sample was analyzed for Cl and Eg. CE.. o Molecular Wt. of Theoretical Chlorine GE CH-GE HgCl S 2 ^ 0 9 . 23 ^ is 382.5 Determination I Determination II Weight of Gooch and AgGl 22.7702 22.9618 ’ ' ” ” alone 22.5760 22.7706 " ” AgCl .1942 .1916 Blanh on reagents .0093 Corrected wt. of AgCl .1849 .0093 .1823 ^ 649„ _ x ,247 4. . ^ _il823 . g . .24 7 4 = q.qsjJ Cl The chlorine v;as determined by fusion in EagOgbomb. The EggGlg formed reduced with Zh E^SO^, the Zn removed by boiling Ea^GOg solution and Cl determined in Usual manner by gravimetric AgEO^. The blank found on Ej,g02 used .1 gram benzoic acid and EEQ^. The Eg v/as obtained by hydrolysis v/ith 1-1 EGl by refluxing and washing the allyl cresol with water, and repeating the hydrolysis and extraction. The method was a modification of the one used by Manchot ( Annalen 421 , page 420). The EaCE and AgEO^ method of analysis was used. I ‘-*t I >!'‘Jfi|f • 'i‘ ■ ***f i|!^4V ■> Vr* .«►•-•' -1 ifi' ' I ^',>5^ ‘ c r: __ , . , ,* , ; . A»- liiojl-:' I ^ * *w. -r t3:ii - • 1 Vi ^ X .-M^ au. r*^ I . A inv ^ E 4 t ri> ’r' . >».’ 1. 4 • « rM 1 .,.v % 4 .* il w * • ~ l»$^ •« ■ M'' •- • /o i *c.m .'*ij ^ ' >-;'i Auir.fefe !frjep''4»|bSTv ^ ♦'>< ' _ 1 ^ % . A*# ;-<5^ 1 ' ' tw.i . , - < It;, ill ii.lPsl ■ '• ■' 'V:V / - ,‘h^ ■ ^ JdUnJA - : '• ^ /r i i- '’, i • “i « -* •• , ‘ '1 . ,* . -1^ «r ».*•'■';•• - , - 4 irf V i :.|a^v-.6’*W /-' ^ 1 ^ ■ ■' , . '■■■■■ / ,?4jri* - K;lv ; ..MuW -: -^ ' /?j' g ga^ ( pMj r-;Ba^ ga. ’ t ') ja a «»4 * a^5 i ! •■• ■ ^7^ '-iaa -7- CH, Mercury in CHg-OE-GHgiigGl Stock solution ITaCn, 12 grams to 500 c.c. of H O 125 c.c. of stock to 100 c.c. for standard solution. Standard used HgGl crys tallyzed from HpO twice, once from absolute alcohol and dried at 110^; .5 grams of HgCl^ titrat- ed with ITaGn. AgHOg solution 3 grams to 600 c.c. Standardization .5 gram EgGl^ .2691 of Eg. 70.71 of NaOn used against .3691 Eg. 1 c.c. .00522 Eg 1 c.c. of AgEOg 1.44 EaCii 80 c.c. of EaOn used. Back titration AgMOg 6.96 c.c. EaGH used by Eg 70.71 .5 of CH^-GE-GH EgGl 0 Eg Theoretical 70 c.c 14.05 49.71 49.71 . of EaGE used of AgEO,- used for back titration c.c. of EaGE used by Eg. X .00522 . 51.91 ^ Eg found. 52 . 28 ?^ " . ■ ■'» ft-' ■ • , - I m ■ i ri wftrj i ra 'i i 1"'t n r n-1 l i rw 9-1 'Vr ^ \ .1, ..'•.■'V IP. ' -•■-■ ?;■> • : j, 't .n W/' ^iV;. ;' *•/.■.,..• 0^*4 , ,: AWM'^ t' I ■ • 1 -fc • ' ri ' « • t ' '' 'V ^ j * '* ' fc' V *■'' '- ' ■ '■' ^ ^'' '' ' . -.'f ■ ' i . ^t %. «■ r ;, .0 ♦ V Vi O' .'-»tKi.‘ 1c- ,. .rt'’ • V -wf.*: « uWr I \. ■• '-■ '- ' ''f . ,.1,^ in ■ .-’\4i^* " Bp i - • , V ., i.'i . » W-i . t* • ■' ►A ' ..... / ■«■: 'rV ■ WJn ■2^^'* f mfr ' 4 * * V Vi- < V' ji * Y 4 T _ ■ t , . .. , *ii ' b,r..n.4 ix^ M ' ,fe '■ » '. ■''^^'?:-V-' .fc • .^4 :'■ y .'ft 1 . ,,.y^ > u4iBaHH*%UW¥iidM«^ i‘.4 1 » J «,ki;^>i/ jiv ^ :* ' ;,.. <*«. ,, ;^ac.rt j iV ''!S . ;’ A,f! mimmm^^'- : %' >'shh f i' fj® ■'ft' S.A fv^.'.u I &/;rii.cr^.L; .Hii- *, ; lU '1 '*>' ■®ij. J' < ' ' vj ,.../*' V, ^^^,^Uli£)^..tL■A^^^^ ._•** *^ ' ' ■ '" !• C.-P' " 't B' , ,< :»■ .in'Cy. .......»»., Ml,!, . ' '•* ,• V ■ J-w' ' - 8 - Prepar at ion of ortho Cresol The raaterial was r^ade in a similar manner to the ptra compound; and it was purified in a similar manner. Yield 83 grams from 100 of ortho cresol. Per cent yield 63 io* Preparation of the Ortho Tolyl Mercurous chloride Purfurane E'ive grams of 1-methyl- £-hydroxy-3-allyl-henzene was added to 9.2 grams of HgOlg dissolved in 250 c.c. of KgO. Rapid mechanical agitation was used for seven hours. An. oily serai solid "body resell ted which was dried over CaClg. The material was purified by washing with ice cold ether, and drying the amorphous powder which resulted. The powder was crystallized three times from absolute alcohol. Yield of crystals 6.2 grams. II. P. 88°-89° Analytical Data .5 gram of OHg-CK-CHgEgCl Theoretical Hg 52.28/^ 1 c.c. of Standard ITaCN .00522 gm. of Hg 1 c.c. of AgllOg 1.44 of llaCH 55.0 c.c. of llaOlT 5.1 c.c. of AgliOg back titration -9- IJaCU used to titrate Kg 48.i54 48.34 X .005££ 6 - 55 c.c, of IlaOK 4*£V c*c. of AgKOg FaOlT to titrate Hg 48.84 X .005££ 5 ' Molecular weight 50.46 io Hg ■ Deter min ation II 48.84 50.98 io Hg ^ 0 CH2-GH-CH2HgCl 38£.5 Prepar a tion of Alljl Organic Mercurous Sulphates from the Allyl Qresols Pive grams of 1-me thy 1-3-ally l-4-hydroxy-'beniiene was added to 10 grams of HgSO^ dissolved in £50 c.c. of 8 ^ HgSO^. The mixture was stirred for seven hours. The material formed was granular and Vv’hite; it ?/as v/ashed and dried. It v/eighed 14 grams, and proved insoluble in H^O, GHgOH, GgHgOH, GH^GOGHg, GHgCHgCEgGH^OH and GH^GOgH. Ho criterion of purity w'-as taken. The Preparation of A l lyl Organic Mercuro u s Sulphates from the Allyl Gresol s. Pive grams of l-methyl-£-hydroxy-3-allyl benzene was stirred with 10 grams of HgSO^ dissolved in £50 c.c. of ■! f > f •,1 •l (. K I »' ti - 10 - 8/0 material v;as stirred for 6 hours; it vms a ■blach gummy mass. The gurae like material was washed vd.th ether and a slate colored powder was obtained. Yield 3.0 grams. Prepa ra tion of the Ally Organic Merouous Acetat es from The Ally Ore sols Seven grams of GH and 15.1 grams of OH GH^-GH-GHg Hg(Ac)^ were agitated in 200 c.c. of S GHgOOgH for 4 hours- A pinkish lAhite pov/der resulted. Dry v/eight 16 grams. It dissolved in alcohol to a syrup; the alcohol removed by blowing air over the surface of the solution ( Boiling caused hydrolysis). The semi crystalline material obtained was washed with ice cold-aether; an amorphous powder being left. This was crystallised from alcohol at -10°. Weight 6.2 grams. i/I.P. 109® - 110.5®. The wash ether gave a residue of 3.3grams of syrup- like material . Molecular Wt. of Analyti cal Data GE^-GK-CH 2 HgAc (?) » 396 Theoretical Hg = 50.50 °Jo Hydrolysed v/ith dilute EGl method followed identical with previous determina tions. V . V* » IT v,V 4 |SJ- *- * * ^ M •, ' '^**U , 'I ^'IQ' .'Hj # 0 J y- £# 4 .. " 'L -.ij H ..3f V V ft. , 'ir li i/ T : ♦ . ■*'). ;W ' :iJ [r!lwi j» a w p^ fi< BtM|awawww>g'ai ^ ' .u w » ' ' 'V' . . ‘*.ii . 'C.) . • j- .v4 ^T'>T-j^i^ff ‘,i6. 'Vr.4it.vit' ■ .'■ ■ nu V. . < • ' . ' , ‘ * V • HKi • • ( ' ' k vT «^fk!' £i^- -lE- The Preparation of th e Allyl Organic I.'Iorcuous Acetate from All.yl p a ra-QresoI Seven grams of 1- me thy 1-3- ally 1-4- hydroxy benzene was stirred in tlie same concen tration of Hg(ii.c) as in the prev- ious experiment. A sticky semi-solid resulted, that v/as removed from the flask by dissolving in alcohol. The alcohol was evaporated off at 45° by a current of air; the material obtained, 11 grams, v/as washed twice with ether at 0°; then dissolved in alcohol from v/lich it could not be removed by chilling. The alcohol was again evaporated by a current of air, and the material washed v/ith ether, v/hen taken into solution in alcohol and chilled to -10° a semi-ci^'stalline mass v/as obtained. Yield £.82 grams. Ll.ir. 149° - 150°. rrepai^tion of the Iodides from the Acetates \- Three grams of allyl orthocresol mercurous acetate compound was treated with 1.3 grams of ICE, the mixture v/as shaken for three hours and allowed to stand for tun days. The material v/as obtained as a granular body. The material proved very soluble in alcohol; E parts of the solid dissolv- ing in one of alcohol. It was purified by successive ether washings and alcohol purifications. Yield of serni^ ciy^stalline powder 3 grams. LI.P. 65° - 69°. -13- Preparation of the Iodides form the Acetates One and forty-six hundredths grams of ally! para-oresol mercurous acetate Vvas shahen vAth .6 gram of hi in 50c. c. of HgO for three hours and allowed to stand for 2 day s- A gummy material was formed. It v/as v/ashed repeatedly with ether; the residue was an amorphous powder, which v/as very slightly soluble in alcohol or ether. Yield .7 gram. M.r. 108° - 110° r ■I r. 3gaa&«'^'~Trirr^ ■ ‘ ' '..*- . v'l ' ' '»■ BT, . . ,■ ; ■ •■ ; •K,», - , H i 2 i: 0> xfc? - . p ' 4 > ' ■ 'Ct. ‘‘V ' *^ ,' ‘' ‘- ^ A <\ ^ - i \) t ‘''^ nvfu - « i |^4 ,,^''*>■^4 ^ 1 ^®*" *‘ 4-|8 •■ G ’.'i-J- ^ " * •*-' ' . *’^‘i®p.^ I ' i '*1 ., '>fSlY ..IV ■(«■ ’ .1 A ,-k^^':t'' J « :’ i ' 4 .pp#. i! • - ’ ■«— — * ' • ''■Tl 'i ' '-TiL W VIBI^Br*4r - 14 - GOHGLUSIOIT The vvork done has shOvvn ttiat organic mercury compounds are formed from the allyl cresols as from the allyl phenols. The purification of the acetates, and iodides from from them, is difficult, by reason of the nature of the material, and the lov/ yield of semi- crystalline powder obtained.