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This t hesis by . h a s b e e n u s e d b y the f o l l o w i n g / p e r s o n s , w h o s e s i g n a t u r e s a t t e s t t h e i r a c c e p t a n c e o f t he a b o v e r e s t r i c t i o n s . its A patrons L ibrary which borrows is e x p e c t e d to s e c u r e NAME AND ADDRESS . t h i s t h e s i s f o r u s e by the s i g n a t u r e of e a c h u s e r . DATE NORTHWESTERN UNIVERSITY THE OXIDATION OP DIOXENE AND RELATED COMPOUNDS BY MERCURIC ACETATE A DISSERTATION SUBMITTED TO THE GRADUATE SCHOOL IN PARTIAL FULFILLMENT OF THE REQUIREMENTS for tlie degree DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMISTRY BY GEORGE HERBERT KALB EVANSTON, ILLINOIS AUGUST, 1940 P ro Q u e s t N u m b e r: 10101570 All rights re s e rv e d INFO RM A TIO N TO ALL USERS T he q u a lity o f this re p ro d u c tio n is d e p e n d e n t u p o n th e q u a lity o f th e c o p y s u b m itte d . In th e unlikely e v e n t th a t th e a u th o r d id n o t s e n d a c o m p le te m a n u sc rip t a n d th e r e a re missing p a g e s , th e s e will b e n o te d . Also, if m a te ria l h a d to b e re m o v e d , a n o te will in d ic a te th e d e le tio n . uest P ro Q u est 10101570 P ublished b y P ro Q u e s t LLC (2016). C o p y rig h t o f t h e Dissertation is h e ld by th e A utho r. All rights re s e rv e d . This w o rk is p r o te c te d a g a in s t u n a u th o rize d c o p y in g u n d e r Title 17, U n ited S tates C o d e M ic ro fo rm Edition © P ro Q u e s t LLC. P ro Q u es t LLC. 789 East E isenhow er P a rk w a y P.O. Box 1346 A n n Arbor, Ml 48106 - 1346 ACKNOWLEDGMENT The author wishes to express his appreciation to Dr. R. K. Summerbell for his constant guidance, his valuable sug gestions and his encouragement during the course of this investigation. PREFACE This investigation is a study of the reactions of vinyl-type ethers with mercuric acetate, silver acetate and cupric acetate. These ethers are unique In their ability to reduce mercuric acetate and silver acetate in aqueous and non-aqueous solvents. In addition an attempt will be made to correlate the reactions studied in this Investigation with similar reac tions recorded in the literature. Throughout this discussion dioxane will be used to designate 1,4-dioxane. The hexagon will be used to denote the benzene ring, unless otherwise noted. TABLE OF CONTENTS page I. HISTORICAL 1. 2. 3. 4. II. Reactions of Olefinic C o m p o u n d s ..... 1 Reactions of Aromatic Compounds . . . . . Reactions of Heterocyclic Compounds . . . Miscellaneous Oxidizing Reactions of Mercury Salts on Organic Compounds . . 19 DISCUSSION OF RESULTS A. Reactions of Dioxene 1* 2. B. C. D. E. F. G. III. 15 16 Reactions in W a t e r .................. Reactions in Various Solvents . . . . Reaction of Reaction of Reactions of Reactions of Reaction of Reaction of 26 31 Vinyl E t h e r ............. 42 <? -Ethylvinyl n-Butyl Ether . 42 Isomeric Propenylanisoles • 44 (A>-Ethoxystyrene . . . . . . 47 Phenyl D i o x a n e ...... .... . 49 D i o x a d i e n e .............. 50 EXPERIMENTAL A. Reactions of Dioxene 1. 2. Preparation of D i o x e n e .............. 51 Reaction of Dioxene with Mercuric Acetate (mol for mol) In water . . 51 3. Reaction of Dioxene with Mercuric Acetate (one mol of dioxene to two 53 mols of salt) In W a t e r ....... 4. Reaction of Dioxene with Mercuric Acetate in M e t h a n o l ......... .... . 54 5. Reaction of Dioxene with Mercuric Acetate in Benzene . ........... 55 6 . Reaction of Dioxene with Mercuric Acetate without Solvent ........... 57 7. Reactions of Silver Acetate with Dioxene .................. 58 8 . Reactions of Cupric Acetate with D i o x e n e ......................... 59 B. Reactions with Vinyl E t h e r ......... C. Reactions with # -Ethylvinyl n-Butyl Ether 1. 2. 3. 59 Preparation of the E t h e r ........... 60 Reactions with Mercuric Acetate in Methanol and W a t e r ............ 62 Reaction with Silver Acetate in Benzene 62 ii. D. Reaction with. o-Propenylanisole 1. 2. E. IV. V. 65 Preparation of m-Propenylanisole . * Reaction of m-Propenylanisole with Aqvieous Mercuric Acetate . . . . . 66 70 Reaction with p-Propenylanisole . . . . . Reaction with Eugenol Methyl Ether ... Reaction with Isoeugenol Methyl Ether . . Reactions with -Ethoxystyrene 71 72 73 1. 2. 73 Preparation of -Ethoxystyrene . . . Mercuriation of tv -Ethoxystyrene with Mercuric Acetate (mol for mol) Mercuriation of w -Ethoxystyrene with Mercuric Acetate (two mols of salt to one mol of the styrene) 75 Reaction of Phenyldioxene ............... Reaction of D i o x a d i e n e .................. 75 76 3. J. K. 63 Reaction with m-Propenylanisole 1. 2. F. G-. H. I. Preparation of o-Propenylanisole . . Reaction of o-Propenylanisole with Mercuric Acetate and Silver Acetate 74 S U M M A R Y ................................. 78 V I T A ........................................... 80 j i I i I ( i HISTORICAL Reactions of Olefinic Compounds with Mercuric Salts i As early as 1898, Deniges showed that certain olefins, for example, hutylene, react with mercuric sulfate in acid solutions to give mercury-containing compounds. These mer- curials were described as yellow solids which react with 8 mineral acids to regenerate the olefin. Deniges found that unsaturated hydrocarbons in general react to form mercuria3.s. Aromatic compounds, including benzene and thiophene, were also shown to react with mercuric salts. Hofmann, et al, carried on an exhaustive investigation on the reaction of several simpler olefins with mercuric salts. They found that five distinct types of mercury-containing coms pounds could be prepared from ethylene. When ethylene is passed into a saturated solution of mercuric chloride, 2-chloro mercuri-1-ethanol (I) is obtained. CHa CHS HgCl OH I When ethylene is bubbled into a nearly neutral solution of mercuric sulfate, formed. a compound, C 6H 10(S04 )gO^Hg^ (II), is When this substance is reacted with a solution of potassium chloride, 2-chloromercuriethyl ether (III), is 1 . Deniges, Compt. rend. 126, 2. Deniges, Compt. rend. 1 2 6 , 3. Hofmann and Sand, Ber. 33, (1900). 1145 (1898). 1808 (1898). 1340 (1900); Ibid 55, 2696 obtained. ClHg-CHa-CHa^ j:o C IHg- C H a -CH III Treatment of compound (II) with potassium bromide solution gives the corresponding bromomercurial. These authors found that this bromide forms 3-oxopentamethylene mercury (IV) on treatment with an alkaline stannite solution, Hg .CHg-CHa. > xC H a-CHa C H a=CH-HgI V IV If ethylene is bubbled into a solution of mercuric ni trate, maintained just at the point of precipitation of mer curic oxide by addition of potassium hydroxide in portions during the reaction, a mercurial Is formed. Treating this mercurial with potassium iodide precipitates I odomer cur I ethyl ene (V). 4s j 5 ^6 W i t h propylene, Sand, et al, was able to show that two distinct compounds can be formed with mercuric salts. Typical structures of these compounds are shown by 1-chloromercuri-2-propanol (VI) and 2-bromomercuriisopropyl ether (VII). C H s-CH-CHa | | OH HgCl CHS CH3 I H G ------0 ----- C I | CHa-HgBr C H aHgBr VI VII 4. 5. 6. Hofmann and Sand, Ber. 33, 1354 (1900). Sand and Singer, Ber. 5 5 , 3172 (1902). Sand and Genssler, Ber. 36, 3704 (1903). Using alcohol instead of* water as the solvent introduces j j; 1S the alkoxy group instead of the hydroxy group. i Schrauth and Esser showed that Thus Schoeller, /S-ace toxymer curie thy 1 methyl ‘ ether (VIII) is formed when ethylene is passed into a solution j of mercuric acetate in dry methanol. CHg— *HgC OCHa VIII The structures of the aforementioned types of compound have "been the subject of much debate. Hofmann, Sand, et al, s ,3 , assigned definite structures to the addition compounds, imply ing that the linkage was the type usually encountered in ordinary organic compounds. 3 Manchot and Klug criticized Hofmann*s formulae on the basis of certain general reactions of these mercurials. One of these reactions was the immediate regeneration of the ole fin when mercurials were treated with concentrated mineral acids. These authors preferred to write the organo-mercuri compounds as simple addition compounds where the mercury is held in much the same way as water of crystallization by inor ganic salts. They believed the addition formulation would better account for the rapid reaction with mineral acids. ©, 10 Adams and coworkers prepared a series of benzofuran mercurials that are stable toward acids. 7. 8. 9. 10. Treating o-allyl- Schoeller, Schrauth and Esser, Ber. 46, Manchot and Klug, Ann. 420, 170 (1920T. Adams, Roman and Sperry, J. Amer. Chem. Mills and Adams, I b i d . 45, 1842 (1933). 2864 (1913). S o c . 44, 1781 (1922) phenol with solutions of mercuric salts containing excess acid results in the formation of 2-halomercurimethyldihydrobenzofuran (IX) according to the reaction: / - C H sHgX 0 — CH \pH a IX It is to be noted that the addition follows Markownikoff *s rule. Thus, these authors demonstrated that not all mercur ials are sensitive to mineral acids. Hugel and Hibon, working with higher olefins, were able to advance an hypothesis for the formation of mercury addition compounds. The olefins were found to react faster in methanol than in water. Compounds of the type, CnHsn(OCHs )HgCsH sOs , were obtained using methanol as the solvent. These authors state that the fixation of mercury is essentially related to solvolysis and that In eases where mineral acid salts of mercury are used, it Is more expedient to neutralize the acid as It is formed in the reaction rather than allow the acidity to Increase as the reaction proceeds. Mercuric salts that show no tendency to liberate free acid by solvolysis, for example, mercuric cyanide or mercuric thiocyanates, show no tendency to react. Treating olefIn-mercury complexes with potassium cyanide or potassium thiocyanate results in rapid 11. Hugel and Hibon, Chem. Abstracts 23, 3898 (1929); Chimie et Industrie, 1929, 296. 5* decomposition of the complex into the olefin, mercuric cyanide and the potassium salt of the mineral acid. hypothesis further, To test this these authors allowed 1-hexadecene to react with mercuric acetate using glacial acetic acid as the solvent. On careful treatment of the reaction mixture with water an oil separated. This oil crystallized readily and on analysis was found to conform to the expected C 16H Bf3Hg(C2H sO s )s . Mercuric chloroacetate in chloroacetic acid and mercuric propionate in propionic acid were found to react analogously. Mercuric mineral acid salts do not react in this manner. Mercuric iodoacetate does not react d.irectly with olefin but must be obtained by reacting an organomercuri salt with potassium iodide. The purely inorganic salts must be prepared in a similar manner, and show a remarkable tendency for de composition into mercuric halide and the olefin. Hugel and Hibon found that one of the two acetate groups in the addition compound of mercuric is quite different from the other. acetate and hexadecene It is possible to titrate one acetate group with standard alkali while the other remains fixed. These authors suggest that the structures and reactions of mercurials be written as follows: CieHsa C 16^38 CiqH82 AcO + Hg OAc NaCl----•‘Cl NaOAc Hg OAc where AcO indicates the acetate grouping. xa Marvel, et al, were successfxil in isolating optical 12. Griffith and Marvel, J. Amer. Chem. S o c . 53, 789 (1931); Sandborn and Marvel, I b i d . 4 8 , 1409 (1926jT isomers when mercuric salts were added to cinnamic esters. Thus two isomers of i’-menth.yl ^S-methoxy- ^-bromomercuri-hydro cinnamate (X) were isolated. OCH0 HgBr ■CH----- CH-COOC10H 10 X j Theoretically four isomers are possible. It is not unusual to j find only two isomers, however, as other reactions are known '! ! j that do not give all possible optical isomers. Isolation of !isomers by these authors seems to break down Manchot*s idea of i jcomplex formation. It does not, however, detract from the idea ! IS }of Piccard (special communication to Marvel et al ) who sug1 gested the compounds be written as follows: i 1 H 0 i Xx J H II /Hg !fc=6-C-0-CloH 18 C H a-Cr ! X / i ;where is the coordination center of the molecule. It is to Ibe noted that two optical isomers are possible here. i le Lucas, Hepner and Winstein postulate a “mercurinium i icomplex” as intermediate to the formation of mercurials as iformulated by Hofmann et al. Their theory is based on kinetic ] !studies on the rate of reaction of cyclohexene in carbon tetraIchloride with mercuric nitrate in aqueous nitric acid. !13. | Lucas, Hepner and Winstein, (1939). The J. Amer. Chem. S o c . 61, 3102 data Indicate that two rapid reactions occur, (a) C eH 10 + Hg++ (to) C s H 1o + Kg++ The structure of the CeH 10Hg++ + H a0 = : and C sH loHg0H+ + intermediate they assume H+. iscomposed of the following resonance isomers: H C H ,C+ H Hg + Hg ++ CXH 4-H-e Hg+ G+ H (a) c4 *:h 0 o4 a-h Lj-e c H ,C (*) Hg H C H (c) (d) ++ These isomers then react to form compounds of the type described by Hofmann. This theory, therefore, correlates the theories of Manchot (loc. cit.) and Hofmann,for essentially there is an equilibrium between the hydrocarbon, Manchot* s type of addition compound, and Hofmann*3 type. Substituting a phenyl group for one hydrogen on ethylene apparently does not affect the ability to react with mercury 14 salts. Thus, Manchot obtained a mercurial by shaking styrene with a saturated solution of mercuric acetate. On pouring the reaction mixture into saturated sodium chloride solution, a crystalline compound, 3C8H e •3HgOHCl•HgGls , was precipitated. 16 Nesmeyanov and Freidlind of styrene. isolated several mercurials With one mole of mercuric acetate for each mol of styrene, 2-acetoxymercuri-l-phenyl-ethanol (XI) was obtained The mereurl chloride (m.p. 95-96°) 14. 15. and the mercuri bromide Manchot, Ann. 4 2 0 , 316 (1920). Nesmeyanov and Freidlind, Chem. Abstracts 32, 2912 (1938); J. Gen. Chem. (U.S.S.R.) 7, 2748 (1937). (m.p. 102-105°) were also prepared. The acetate (XI) on reduction with sodium amalgam gave 1-phenylethanol. OH H g C sH 30 2 / ' N A h 4 \ / OH h CH. 1HgC1. \/ m.p. 77-79° XI i HgCl XII With excess mercuric chloride on styrene, compound (XII) was i! j obtained. j is ji Manchot, Haas and Mahrlein investigated the mercuration j j of u> -ethoxystyrene. It was found that mercuration with J ;,i Imercuric acetate was complete in three hours if the reaction j mixture was maintained at 50°. On pouring the mixture into |sodium chloride a substance, C 6H 5-CB=CH0H*2HgC10H, was found I jto separate. j compound Nesmeyanov and Freidlind 16 suggest that Manchot*s was actually of the type shown below. /v; CH-0-CsH e ■CH- The effect of a conjugated carbonyl group was Investigated 1 $ 18 j 10 by Schoeller, Schrauth and Struensee, who isolated two types of mercurials from cinnamic esters, namely, < 16. 17. 18. 19. ^ ^y-CH-CH-COOR1 — <! )P HgCsH _TT_n_ )R sO s find \ .... \CH-CK-C=0 or FFe:-0 OR Hg-0 Manchot, Haas and Mahrlein, Ann. 417, 93 (1918). Schoeller, Schrauth and Struensee, Ber. 43, 695 (1910). Schoeller, Schrauth and Struensee, Ibid. 44, 1432 (1911) Schoeller, Schrauth and Struensee, Ibid. 4 4 , 1048 (1911) 9. ij where R may be H or an alkyl radical depending on the solvent i i ij used. 3 This work was recently verified by Matejka, so who also used ethylene glycol as a solvent in addition to a number of | simpler alcohols. In the case of the glycol, however, it was 'j I found that mercurous acetate was formed. | The reactions of aliphatic double bonds with mercuric ij salts, that have been cited thus far, apparently follow certain j j regularities, i.e., the elements of -HgX and -OR (where R is 1 ij hydrogen or an alkyl radical) add across the oleflnic double | I bond. j This is the typical reaction for a large number of molecules containing an olefinic double bond. Some molecules, | which seem to have the same type of bond, react anomolously j with mercuric acetate reducing mercuric salts to mercurous ! salts while they, themselves are oxidized to glycols. This investigation deals primarily with these anomolous reactions i j so they will be discussed in some detail. ! ! Balbiano, Paolini and coworkers reported on several compounds that caused reduction of mercuric acetate to free i mercury in cold aqueous solution. Since their work is closely j allied to the investigations pursued in this dissertation, ■| I their work will be reported In some detail. j 81,38 | These authors found that,f-pinen& (XIII) reacted j with the strichiometricly equivalent quantity of mercuric ! ; acetate to form 2 - h y d r o x y - 6-keto-1-menthene (XIV). 20. Matejka, Ber. 69B, 274 (1936). I 21. Balbiano, Paolini et al, Ber. 35, 2994 (1902); Atti. R. I Accad. Lincei V, ii, 65 (1902); J.Chem. S o c . 82i, | 808 (1902). | 22. Balbiano, Paolini et al, Ber. 36, 3575 (1903). XIII 0 XIV Camphene (XV) on the other hand reacts to form an addition co m p o u n d . CHS CH l CHa C=CH,8 CH, CH- C-CHS I chb XV Balbiano and Paolini with Nardacci allowed anethol (XVI) to react with aqueous mercuric acetate for one week. They obtained as products free mercury and two isomeric as , 1 - (p-anisyl)-l,2 propanediols (m.p. 62° and 114-115°) (XVI). 'CH CH=CH-CH V C H - CHl l OH OH XVI XVII Methylchavicol 88 (XVIII), on the other hand, reacts with mercuric acetate to form a mercurial soluble in water and alcohol, especially when warmed. 25. The mercurial is actually See also Balbiano, Paolini and de Conno, Atti. R. Accad. Lincei 16, V, i, 477 (1907);, J. Chem. S o c . 9 4 i , 901 (1908) Kolokoloff, Chem. Cent. 1897 , I, 915. a mixture of two isomers which can "be separated by prefer ential solubility of one isomer in absolute ethanol. The ethanol-soluble isomer melts at 81-82°, whereas the insoluble isomer gives an indefinite melting point at about 55°. Re duction of either isomer with zinc and aqueous sodium hydroxide gives methylchavicol. The structures of the two isomeric mer curials are assumed to be 3 - (p-anisyl)-2-chloromercuri-l-propanol (XIX) and 1- (p-anisyl)-3-chloromercuri-2 propanol (XX). /V V och3 C H S-CH=CHS /X \/ OCHs C H S-CH CHS I I HgCl OH QCH3 / s \/ CHg-CH-CH, OH HgCl XVIII XIX Balbiano and Paolini XX prepared the mercury derivatives of methyleugenol (XXI) by evaporating equimolecular quantities of methyleugenol and saturated mercuric acetate on a steam bath. The product was changed into the chloride and the two isomeric mercurichlorides (XXII and XXIII) separated by solu tion in alcohol. OCHi OCH C H S-CH=CHS OCH3 OCH CHo-CH-CHft I I OH HgCl och3 / X OCHi CHo-CH CH2 I I HgCl OH XXI XXII XXIII These authors found that methylisoeugenol (XXIV) reacted to form isomeric glycols and free mercury. These glycols were as obtained previously by Kolokoloff. The melting points of the isomers are 120-121° and 88-89°. 0CH3 OCH CH=CH-CH3 XXIV Manchot found that eugenol (XXV) formed no definite isolable product with mercuric acetate. He concluded from his researches that it is the unsaturated side chain that d e termines the course of the reaction with mercuric acetate, but, irrespective of the position, tially ethylenic in nature. the double bond is essen In support of this idea he ad vanced as an argument the reduction of mercuric acetate by trimethylethylene. Balbiano and Paolini with Luzzi of reactions for safrole (XXVI) 81 reported the same types and isosafrole (XXVII) by the allyl and propenyl ethers mentioned above. 0— CHS 0— CH OH X / 0CHs C H 2-CH=CHS XXV 24. C H S-CH=CHS CH=CH-CHS XXVI XXVII Manchot, Ann. 421, 519 (1919). as given 13. 85 Tsukamoto prepared the chloromercurial of safrole u s ing mercuric acetate, water and sodium chloride. the melting point of the mercurial as 135°. He reported Reaction of the chloromercuri addition product with hydrochloric acid, aqueous sodium sulfide or zinc and potassium hydroxide resulted in re generation of safrole. Iodine in potassium iodide solution gave the iodohydrin (XXVIII) which reacted with dimethyl aniline to form the compound (XXIX). Hydrolysis of the iodohydrin gave the glycol (XXX) which melted at 76°. 0— 0 ---CH e G H ft 0 \ N / / OH I | | G H 3-C K -C H 3 \ X / / OH N - (C H « ) a I | CHa -C H -C H s xxvm ::xxix \ / OH OH C H g-C H -C H g xxx o0 27 Balbiano and coworkers 9 reported that myristicin(XXXI) and Isomyristicin (XXXII) react to form the expected mercurial and glycol,respectively, and that asarone (XXXIII) reacts in the usual manner to form isomeric glycols. 0 C H s0 “ /V CH* ■ v CHS-CH=CHS XXXI 25. 26. 27. 0 — CKa gh3 0 OCH CH« 0 — V C H =C II-C H S XXXII XXXIII Tsukamoto, J. Pharm. S o c . Japan 50, 7 (1930)5 Chem. Abstracts 24, 1853 (1930). Balbiano, Atti. R. Accad. Lincei 1 8 , V, i, 372 (1909); J. Chem. Soc. 961, 401 (1909). Balbiano, Paolini, Nardacci, Tonazzi, Luzzi, Bernardini, Cirelli, Mammola and Vespignani, Atti. R. Accad. Lincei 5, V, i, 515 (1905); J. Chem. Soc. 90i, 186 (1906). Apiol (XXXIV) was found to react normally yielding the £ 1,a £ isomeric mercurials, Isoapiol,(XXXV) on.the. other hand, reacts with mercuric acetate to form a mercurial, possibly 2- ( 2 ,5 dimethoxy-3,4-ethylenedioxyphenyl)-l acetoxymercuri-2propanol (XXXVI), in addition to the expected glycol. GH, 0 CHS 1 2 / \ -0 C H eO- \/ -OCH. 0 I C H e0 £1 3 ££ -CHS '0 — OCHi -0CHs I CH=CE-CHS CH- CH-CH3 HgCgHsOs OH XXXIV XXXV XXXVI This anomolous reaction was explained on the insolubility of the addition compound in the reaction medium. This state ment implies that Balbiano and coworkers believe that the mercury addition compound is the intermediate in glycol formation from the propenyl ethers. In general, therefore, a propenyl compound will react with mercuric acetate to form isomeric glycols, whereas an allyl compound will form isomeric mercury derivatives. £8 , £9 Balbiano and Paolini propenyl and allyl compounds. used this reaction to separate In their researches they were able to separate anethole from methyl chavicole, safrole from K isosafrole, myristAin from isomyristin and apiol from isoapiol 28. 29. Balbiano, Ber. 42, 1502 (1909). Balbiano and Paolini, Atti. R. Accad. Lincei 18, V, i, 372 (1909); J. Chem. Soc. 961, 401 (1909). In these cases only the acetoxymercuri compound of the allyl compound was formed. steam distillation, The propenyl compound was removed by and the allyl compound was regenerated by reaction of the mercurial with zinc and aqueous sodium h y d r o x i d e. so Lauer and Leekley useo the reaction of mercuric acetate to test the completeness of reaction of substituted phenyl allyl ethers into propenyl phenols. The reaction was run on the methyl ether and the merciirous acetate formed was weighed to give a quantitative determination of the amount of propenyl compoimd formed. 2. Reactions of Aromatic Compounds with Mercuric Acetate When benzene is reacted with mercuric acetate at higher temperatures in an appropriate solvent phenylmercurie acetate is formed. 31, S2,SS,34:}B6 Most of the higher homologs can be prepared by reacting the appropriate mercuric salt with the Grignard reagent of the desired compound or by reacting the diaryl mercury with a 37 ,36 mercuric salt. Direct action of toluene with mercuric acetate results in a mixture of ortho and para isomers which can be separat- : 33,34,66,36 ed. 30. 31. 32. 33. 34. 35. 36. 37. 38. Lauer and Leekley, J. Amer. Chem. Soc. 61, 3042 (1939). Otto, J. prakt. Chem. 29, 2 , 136 (18847. Maynard, J. Amer. Chem. Soc. 46, 1511 (1924). Dimroth, Ber. 31, 2154 (1898). Dimroth, I b i d . 5 2 , 758 (1899). Dimroth, I bid. 35, 2853 (1902). Whitmore and Sobatzki, J. Amer. Chem. Soc. 5 5 , 1128 (1933). Hilpert and Gruttner, Ber. 48, 906 (1915). Kunz, Ber. 31, 1528 (1898). 16. The structure of aromatic mercurials is t r i f l e d by phenylmercuric acetate (XXXVII). It is to be noted that these are true substitution compounds and are not merely additions of mercuric salts to the double bond as in the aliphatic com pounds . XXXVII 3. Reaction of Heterocyclic Compounds with Mercuric Acetate Sachs and Eberhartinger mercuripyridine prepared the 3,5-dichloro- (XXXVIII) and the 3-iodomercuripyridine (XXXJX) by heating together pyridine and mercuric acetate at 175-180° for 2*5 hours, solution. and pouring the mixture into sodium chloride Addition of sodium iodide to the mother liquor precipitates the iodo compound. ClHg- -HgCl \ N / XXXVIII -Hgl \ N / (XXXIX) A mercurial is formed when 2-anisylindole is reacted with mercuric acetate in hot ethanol. 40 The mercurial Is given as 3-chloromercuri-2- (p-anisylindole) (XL) after the 39. 40. Sachs and Eberhartinger, Ber. 56B, 2223 (1923); see also McCleland and Wilson, J. Chem. Soc. 1932, 1263. Boehringer and Sohne, German Pat. 236,893 (1910); Chem. Abstracts 6 , 1500 (1912). 17. reaction mixture is poured into sodium chloride solution. (Compare with anethol.) -HgCl ^ QCHa / N N H H XL XZ>H‘ XLI Ciusa and Grillo 41 prepared tetraacetoxymercurifuran hy shaking furan w ith aqueous mercuric acetate. On shaking this mercurial with iodine in potassium iodide solution, tetraiodo- furan is obtained. Gilman and Wright prepared a series of furan mercurials by the direct action of a sodium acetate buffered mercuric chloride solution on several furans. The mercuration proceeds stepwise giving a mixture of 2-chloromercurifuran (XLII), which is soluble in hot ethanol, and 2,5-dichloromercurifuran (XLIII), which is insoluble in hot alcohol. v XLXI -HgCl C l H g - ^ ^j-HgCl XLIII Proof of structure of the mercurial was obtained by pre paring a series of compounds from the mercurifurans. The following reactions were run on the monomercurial: 41. 42. Ciusa and Grillo, Gazz. chim. Ital. 5 7 , 323 (1927); Chem. Abstracts 21, 2686 (1927). Gilman and Wrigh¥7 J. Amer. Chem. Soc. 5£5, 3302 (1933). 18. Reactant Product Yield acetyl chloride 2-furyl methyl ketone 21$ furfuryl chloride difurylmethane iodine in potassium iodide 2-iodofuran me thy 1 sulf at e fur an aqueous sodium thiosulfate 2- 2 »-difurylmercury bromine in carbontetrachloride 9 .5$ 32$ 2-bromofuran 14.5$ In the mercuration of 2-methylfuran an intermediate pro duct analyzing for G sH 6OHQ (OH)Cl 'HgClg was isolated. This Intermediate formed 5—methyl-2-chloromercurifuran on boiling in absolute alcdhol. Summerbell and Umhoefer prepared the dimercurichloride of dioxadiene (XLIV) by reacting dioxadiene with a solution of mercuric chloride buffered with sodium acetate. mercurial showed no definite melting point, The di and was insoluble in alcohol, ether, dioxane, benzene and acetic acid. compound analyzed for C^HgOgHggClg. The The structure of this compound has not been proven, but it is probably the 2,5 or the 2,6 dichloromercuridioxadlene (XLV or XLVI). /°\CH CH CH V XLIV 43. CH ClHg-C / \ CH HC C-HgCl \/ XLV ClHg-C / \ C-HgCl HC CH \/ XLVI Summerbell and Umhoefer, J. Amer. Chem. S o c . 61, 3023 (1939); Umhoefer, Ph. D. Thesis, Northwestern Univer sity, 1938. Heterocyclic compounds which, show aromatic properties react with mercuric salts to form substituted mercurials in much the same manner as simple aromatic compounds. Appar ently the ether grouping in fur an and dioxadiene has no ef fect on the structure of the product obtained in this reac tion, 4. Miscellaneous Oxidizing Reactions of Mercury Salts on Organic Compounds„ As early as 1892 Tafel used mercuric acetate and sil ver acetate at higher temper atures as a dehydrogen at ing agent. Thus, piperidine was converted into pyridine, coniine (XLVII) was converted into conyrine (XLVTII) and tetrahydroquinoline was converted into quinoline by prolonged action of mercuric acetate in a sealed tube. h2 H3 Ho -CHa-CHs-CHs \ HH/ XLVII / - C H o-C K o-C H . 11 XLVIII 45 Leys * found that mercuric acetate reacted with the unsaturated acids, crotonlc, oleic, elaidic and linoleic, 44. 45. 46. to Tafel, Ber. 25, 1619 (1892). Leys, Bull, s o c . chim. 4 , 1 , 262 (1907); Chem.Abstracts 1, 1689 (1907). Leys, Bull. Soc. chim. 4 , I, 633 (1907); Chem. Abstracts 1 , 2683 (1907). form mercurous acetate and mercury containing organic com pounds. acids* Their structures were not proved. Saturated fatty on the other hand* formed no mercurous acetate. Leys stated further that the main reaction was fixation of mer cury to the double bond and formation of the salts. ulated, however, He post an ethylene oxide type of binding to account for reduction of the mercuric salt. 4.7 Goswarni and Ganguly reacted glycerol with mercuric chloride in a sealed tube for 3 hours at 180° and obtained glyceraldehyde, formaldehyde and aorolein in addition to mer curous chloride. 4:3 Zappi reacted a series of compounds* capable of enol- izing* with mercurous nitrate in aqueous solution. In all the enolic compounds tested* free mercury was obtained. This author considered at first the possibility of salt formation wit h substances like the enol of acetoacetic ester which would then decompose to give the mercuric salt and free mer cury. Apparently this is not the case* however* for all mercurous salts would be anticipated to give free mercury and this Is contrary to experiment. The reagent is quite sensitive* for it has been found to work with slightly enolized substances like butanone* acetophenone and formamlde. It is interesting that phloroglucinol and isoeugenol as well as eugenol give this test. 47. 48. The reactive structures which Goswarni and Ganguly, Chem. Abstracts 24, 1048 (1930); J. Indian Chem. Soc. j6, 711 (1929). Zappi* Bull. soc. chim. 51, 54 (1933). give the test are listed as: OH -C=C OH i U i o oII II te! a W (a) enolic substances (t>) amides (o) isonitites isocyanates G=C=HH (e) isothiocyanates S=C=NH (£) hydroc arbons R-CHS-CH=CHS (a) R-CHa-CH=CHR R-CH CHR 49 Zappi and Williams showed by absorption measurements that* in the cases tested, the enolic form is present in the substances that give mercury from mercurous nitrate. itional support to the hypothesis, Add that the enolic form is responsible for the reduction of mercurous nitrate, is based on the non-re action of e thy If ormate, ethyl oxalate and ethyl acetate. Ethy If ormate and ethyl oxalate are known to be good reducing agents. These compounds do not give free mercury, however, because they are not capable of existing in an enol— ic form. Dansi and Sempronj found that methyl ethyl ketone, methyl hexyl ketone and methyl nonyl ketone give the Zappi reaction. curials, 49. 50. Yellow intermediate compounds, assumed to be m e r are formed when p-tolyl methyl ketone and ace to- Zappi and Williams, Bull. soc. c h i m . 51, 1258 (1932). Dansi and Sempronj, Chem. Abstracts 28, 1331 (1 934;, Grazz. chim. ital. 6 5 , 560 (1933). phenone are made to react with, mercurous nitrate. These yellow solids decompose on heating to give nitrous fumes and free mercury* 51 Zappi and Manini explain the reduction on the basis of an equilibrium between mercurous nitrate, mercuric nitrate and free mercury, according to the equation HSa(NOe )a — Hg + Hg(NOa )a Mercuric nitrate is assumed to react with the e n d to form relatively insoluble complexes, to the right* thus driving the equilibrium Isolation of the products of the reaction would determine the correctness of this hypothesis. Connor and Van Campen reported that mercuric chloride or mercuric acetate in alcoholic solution forms white pre cipitates with enolic-type compounds. Small amounts of so dium ethoxide are added to the reaction mixture, presumably to increase the amount of enolic form. The compounds tested are similar to those of Zappi (loc. cit. ) but the reaction is more limited in scope. It works well only on neutral compounds containing carbon, hydrogen and oxygen. The test is specific for structures, 0 II H- c -C-R XLIX 51. 52. and R0 iif X-CH-C-OR L Zappi andManini, Chem. Abstracts 33, 2063(1939);, Chem. Zent. (1939), I,3427; Anales. assoc, quin, argentina 26, 89 (1938). Connor and Van Campen, J. Amer. Chem. Soc. 58, 1131 (1936). 23. where Y is a labilizing group and R is hydrogen, group, an alkyl or an aryl group. These authors postulate the formation or mercury com pounds whose structures have not "been determined. list, however, They do the following structure types as possibil ities . COOE+ Hg=C HO-Hg-CH- (COOE+)s x COOE+ LI LI I (GlHg)s-G-(GOOE+)s E+OOC. ^COOE+ CH-Hg-CH E+OOC ^COOEH- LIII LIV GOOE+ COOE+ ( I — C Hg — C Hg I I COOE+ COOE+ COOE+ I C --I COOE+ LV 5sa Indovina and Manfroi re anted ascorbic acid (LVI) w it h mercuric chloride. A compound, C 6H 60 6 , and mercurous chloride were isolated as the products. The reaction is of third order and reaches completion in 36 hours at room temperature. 53b Mercuric acetate can also be used for this reaction. Ascorbic acid is an enediol type compound, so that this re action may be related to the Zappi reaction. The reaction is reversible so that the compound C QH 606 can be converted ba.ck 53. a. Indovina and Manfroi, Gazz. chim. ital. .69* 117 (1939). b. Emmerie, Bioehem. J. 28, 268 (1934). HO-0=0-015, I \ HC-0-C=0 I HO-C-H I GHgOH LVI to ascorbic acid by treatment with, hydrogen sulfide. Rao and Seshadri found that benzoin is oxidized to benzil by the action of mercuric acetate in water or abso lute methanol. 5. Reaction of Olefins with Silver Acetate and Copper Acetate 55, 56 Lucas and coworkers have shown that silver ions form a nrapid and reversible” coordination complex with ole fins. The coordination compound is assumed to be a reson ating structure intermediate between the following three isomers: C C /+ / |\ Ag (a) x C C / \ +\ / X C = C / r "\ Ag Ag (b) (c) Several monoolefins, diolefins and the unsaturated ox ygen - containing compounds listed below - have been tested and have been found to form coordination complexes. 54. 55. 56. Rao and Seshadri, P r o c . Indian Acad. Scl. 11A, 25 (1940). Eberz, Welge, Yost and Lucas, J. Amer. Chem. Soc. 59, 45 (1937). WTnstein and Lucas, J. Amer. Chem. Soc. 60, S36 (1938). allyl alcohol crotonic acid crotyl alcohol phenol croton aldehyde W i t h biallyl and dicyclopentadiene solid silver complexes were Isolated. Silver analyses of the solid complexes In dicate a 1 to 1 molecular ratio: of organic radical to sil ver salt. DISCUSSION 4 ;3 Summerbell and Umhoefer found that dioxadiene re acts with mercuric acetate to form a dimercurial similar to that obtained from fur an. These substances (dioxadiene and fur an) are essentially aromatic in character so that the reaction is one of substitution. Evidences of the aro matic ity can be seen in their stability and the variation of boiling point with increasing unsaturation. A table of the boiling points of these series with the ethyl ether series follows: Boiling Point (760mm. pressure) in C° Dioxane 101° Ethyl Ether 34.5° Tetrahydrofuran Dioxene 94° Ethyl Vinyl Ether 35.7° Dihydrofur an 67° Dioxadiene 75° Vinyl Ether 32° 28° Furan 65° The most aromatic compounds have the lowest boiling point in all of the cases cited. Dioxadiene, however, shows at least one usual property of aliphatic compounds in its ability to add two atoms of bromine or four atoms of chlo rine. This property is not surprising, for benzene can be made to add six molecules of bromine under the correct conditions. It is interesting that the introduction of one double bond into the dioxane nucleus decreases the boil ing point, whereas in the series the boiling point is in- creased. This phenomenon would seem to indicate the pos sibility of weakly aromatic properties in dioxene. In view of these facts it seemed desirable to prepare a mer curial of dioxene and to use this mercurial in the prep aration of dioxane derivatives which had not been previ ously reported. The potentialities of this approach are evident from the work on fur an by Gilman and Wright. £3 In the first experiments equimolar quantities of dioxene and mercuric acetate solution were mixed together. Within a minute a white precipitate was formed, and after approximately 15 minutes the precipitate began to turn greyish. The reaction was accompanied by the liberation of appreciable quantities of heat. After 45 minutes the precipitate, which was grey-black in color at this point, was filtered from the solution and allowed to stand In the filter paper overnight. The next day a small globule of mercury was noted in the filter paper, indicating that dioxene had reduced the mercuric mercury to the free met al. In another experiment, using two mols of aqueous mer curic acetate for each mol of dioxene, the same phenome non was observed, except that the end product was mercur ous acetate instead of free mercury. Accompanying this reduction was the oxidation of dioxene to glyoxal and 28. ethylene glycol. Because of the extreme solubility of these two substances in water it was necessary to iso late them as the osazone and dibenzoate respectively. Apparently, the double bond in dioxene is quite suscep tible to oxidation by mercuric salts, for the reaction occurs very rapidly at room temperatures. These data initiated a search of the literature to discover whether such phenomena had been observed previ2 3, 2 a ously. It was discovered that Balbiano and coworkers, working with propenyl anisoles, had obtained reduction of mercuric acetate. In all the cases investigated, at least one methoxy group was ortho or para to the propenyl group on the benzene ring. The active structures may be considered as: OCH OCH CH-CH-CH, CH=CH-CH 57 By applying the principle of vinylogy a profound sim ilarity between the structure of these compounds and di oxene can be seen. 57. This principle states that the in- Fuson, Chem. Rev., 16, 1 (1955). troduction of a -GH=CH- group between a system A-B, in w hich A is the activating group, to form, A-C=C-B, the activity of group B remains essentially unchanged. Re moving the -C=C- bond in portions 1 and 2, we obtain the basic structure of the group OCHa / C C n (a) (b) Similarly by removal of the two -C=C- groups compound the same structure (b) is obtained. in the para One can see, therefore, that the compounds of Balbiano and co workers are intrinsically vinyl ethers, and that the ac tive structure is -0-C=C-. Dioxene has a similar struc ture, except that there are two oxygen atoms the double bond. to activate The activating influence of these two ether linkages readily explains the rapidity of reduction of mercuric mercury when compared with the methoxy propenylbenzenes, which usually require from ten days to two weeks to progress to the same point that dioxene attains in 45 minutes. The difference in solubility is probably also of prime consideration. 30 To discover wh.eth.er the oxidation of dioxene was the only reaction, mercuric acetate and dioxene in water were reacted at room temperature to obtain maximum yields. W i t h one mol c of the acetate for each mol u of dioxene, the mercury was obtained in 97.3$ of theoretical yield, glyoxal (as the osazone) in 95*5$ of theoretical yield and ethylene glycol (as the dibenzoate) in 87.3$ of theoretical yields. Using two mols of the acetate per mol of dioxene, the yield of mercurous acetate was 97.5$ of theoretical, glyoxal osazone was 98.6$. In both of these reactions the mixtures were shaken for .5 hour. On the basis of these results it seems that the reaction of dioxene with mercuric acetate is unidirectional. Dioxene is apparently a better reducing agent than glyoxal for the aldehyde was isolated as one of the pro ducts of the reaction even though an equimolar quantity of mercurous acetate was present. The reaction may be formu^ lated as follows: 0 H SC | H n CH-OAe CH II + + Hg(0Ao)a H 8C CH Hg° CH-0Ac (1) CH-OH CHO + + C H a0H CHO H eC CH-OH 2H0Ac The reaction mixture is acid by hydrolysis of the mercuric acetate. It is possible that the diacetate may have a fi nite existence in aqueous solution for it may be reerystalllzed from water. In one experiment to determine the solu bility of the diacetate and its reaction with phenylhydrozine, it was found that the diacetate would just dissolve in the amount of water used in the mercuric acetate experi ments and that there is no noticeable effect on the rate of precipitation of the osazone. It was found, also, that these reactions proceed in methanol solution. The rate is about as rapid as in aque ous solution. In an attempt to discover the true nature of this oxi dation several experiments were performed in dry benzene. It was found that no reaction occurred when equimolar quan tities of mercuric acetate and dioxene in benzene were shaken for two days. In another experiment equimolar quan tities of dioxene and mercuric acetate in benzene were re fluxed for two days, whereupon a black precipitate of mer cury was observed. After removal of the mercury by filtra tion and distillation of the benzene, the residue was frac tionally distilled. A few drops of a substance boiling at 158° under 25mm. pressure. Hydrolysis of this fraction gave a solution which was acid to litmus. Treatment of the solution with an aqueous solution of phenylhydrazine and acetic acid gave a substance melting at 160°. point of glyoxal osazone is given as 170°. The melting The quantity obtained was too small for recrystallization, but it seems that some glyoxal was obtained in hydrolysis of this frac tion. Several other experiments patterned after the out line given above were performed and in all cases free mer cury was obtained but in no case were definite organic pro ducts isolated. In anhydrous media the reaction should follow the reaction shown below. CHa CH« || CH + CHS CH-OAc CHa CH-OAc Hg (0Ac )s + Hg° (2) In all the experiments where benzene was used as a solvent the reactants were dried as well as possible. Benzene was dried over calcium chloride and the mercuric acetate In a vacuum dessicator prior to use. In an effort to Isolate the 2,3- diacetate of dioxane, which should be one produet of the reaction under anhydrous conditions, equimolar quantities of dioxene and mercuric acetate were mixed without any solvent. duction period of about ten minutes, ous reaction, There was an in after which a vigor accompanied by the evolution of considerable heat, occurred. At the end of one—half hour the solid In the flask was grey— clack In color. After shaking the mix ture overnight an additional amount of dioxene was added. The mixture was shaken for one week and then allowed to stand for one week. After removal of the precipitate and excess dioxene, the residue, which smelled strongly of ace tic acid, was fractionated. A small quantity of a thick oil, boiling at 110°-130° under 7mm. pressure (2,3-diaceto dioxane boils at 150°-155° under I7mm. pressure), lected. was col Water was added to this material and, after long cooling in an Ice bath, long needle-like crystals of the diacetate were obtained. These crystals melted at 105.5- 106° and gave no melting point depression when a mixed melting point with a known sample of the diacetate was de termined. This latter evidence gives, therefore, some basis for writing 2,3-diacetate of dioxane as an intermediate in equation (1). It might be argued that the reactions in anhydrous media follow, a different path than they do in water solution, because the rate is so different. This difference can be attributed to the lesser solubility of mercuric acetate in the anhydrous media. From this series of experiments one must assume that the reactions of dioxene with mercuric acetate are due to the vinyl ether grouping in dioxene and not to any enolic form which might result from hydrolysis as shown below. 58. J:’ Boeseken, Tellegen and Henriquez, J. Amer. Chem. Soc. 54, 3777 (1932); ibid. 55, 1284 (1933). Tli© double bond Is apparently activated by the ether link ages, to such a degree that it is easily attacked by mercuric acetate, 49,81 Zappi and coworkers, 50 and Dansi and Sempronj have demonstrated that compounds, capable of existing in enolic forms, reduce mercurous nitrate to free mercury. They postu late the enolic structure as being the active grouping. Di oxene may be considered as the cyclic ether of an enediol with a grouping similar to that of the enolic forms of acetoacetic ester or malonic ester. Thus we can write hypotheti cally: (4) C H 3-OH | C H a-OE + HO-CH | HO-CH ^ CHa-G-CH | || CHa-O-CH + 2Ha0 to demonstrate the similarity between dioxene and the enol of acetoacetic acid (LVIX). OH 0 I II C H a — G = G H - C — 0E+ LVII Mercuric mercury is a better oxidizing agent than mercurous mercury (assuming equivalent activities of the ions in solu tion) and, therefore, one would anticipate that all enolic structures would reduce mercuric mercury, experimentally. This is not found Connor and Van Campen6* showed that enols in alcoholic solution react, m the presence of small amounts of sodium ©thoxide, to form mercury—containing compounds. The sodium ethoxide is added to increase enolization. The results of these other workers seem to he in disagreement with the work reported in this investigation. planations are possible. Several ex In the first place the conditions of Connor and Van Campen’s reactions are quite different from the conditions of the reactions reported in this disserts tion. C onnor’s reaction is carried out in an alkaline medium whereas the reactions reported here are all in acid media. Zappi’s reactions are carried out in 10# nitric acid solution, so these conditions are also unlike the conditions in this experiment. It might he argued that dioxene is more active due to the presence of two ether linkages activating the double bond. This; is probably true, but the reduction of mercury by ortho and para propenylanisoles (which will be discussed later) then becomes an anomaly. Apparently the differences In activity require more profound study before any plausible explanation can be made. A discussion of the reactions of dioxene with silver acetate and cupric acetate will throw some light on these apparent divergences in reactions. W h e n dioxene is shaken with a solution of silver acetate in aqueous solution reduction of the silver to the free metal occurs. The reaction is, however, much slower than with mer curic salts. After being shaken for four days the weight of the precipitate was 5.624 g. whereas the theoretical weight of silver for quantitative reaction was 4.76 g. The osazone of glyoxal was isolated in 14.9# of theoretical yield. Di oxene reacts with silver acetate in dry benzene, but the mix ture must be held at the refluxing temperature of benzene. In one experiment silver acetate and a benzene solution of dioxene were shaken for three days. A slight brown precipi tate was noted but the quantity was quite small. W i t h cupric acetate in aqueous solution, using two mols or one mol per mol of dioxene, no precipitate of copper was obtained after shaking the mixture for thirteen days. These results are in accord with the findings of Lucas 2.3, 53, 66 and coworkers if an Intermediate coordination compound is postulated as the mechanism. They reported that in general olefins coordinate more rapidly with mercuric salts than they do with silver salts, and that cupric ions do not coordinate with an olefinic double bond. These comparisons suggest that some sort of coordination complex may be intermediate In the oxidation of these vinyl ethers. Lucas et al believe that these complexes exist in equilibrium with the olefin, the salt, and (In the case of mercury) the true mercurial. jLS On the assumption that there is a common Intermediate for oxidation and mercuration, the anomalous reaction of isoapiol to form a mercurial besides the expected reducing of mercury, can be explained. L u cas’ experiments dealt only with aqueous solutions of the metal salts. The work of Hugel and Hibon,1* however, showed that complexes are formed in non-aqueous solu tions also. Assuming a mechanism similar to that of Lucas (loc. cit.) involves some rather peculiar transformations. Thus we could write: ^ 0 H ?H s 9 CHa G \ •• O -0:C:" .. , - 0 :C * ^ H (a) „ HgOAc* ^ -0:C:Hg:0: -Q:C+ &'C " I H CH 0 (b) H -0 :C :Eg:0 : 0:c£:0Tc+ H H (c) H __ ^ -0:c£g£*Sfc: H -0 :C:Hg:0® ^ -0 :C:6 :' C+ CHa H (d) ^ oh8 - 0 :C:6 :C-CH3 h (e) (f) H H —OsG**" ;0s ** ** -OsCsC:C-CH0 + Hff° •• •OAc > —OtCsO*CsCHs ** -0:C:§!C:CHs .. ** H H (s ) .0= * I I o I11) ^ 38. The transf ormations to compound (f) are well known. 5© Prom intermediate (f), which is essentially similar to Lucas* resonance isomers, two paths can be taken. Mercury can be forced from the intermediate and an acetate radical can enter to assume its position, or the acetate group can attach itself to the mercury as shown below. ■' 5 0:C:Hg+ -0sC:0:C :CHS «« H H 0 -0:C:Hg:Q-fi-CHa :m0: -0:C:£:C-CH3 H (£) (1 ) This is the path taken by isoapiol when it forms a mercurial. The step from (f) to (g) is the weakest point of this formulation. Mercury would then draw the electrons away from the carbon, forming the free mercury and leaving the carbon atom positive. The negative acetate ion would be attracted to this carbon and would share its electrons forming the di acetate, With two mols of mercuric acetate, the excess mer curic acetate would react with the free mercury to form mer curous acetate. A similar explanation can be used with silver acetate. Another explanation of the reaction is the assumption that mercuration and oxidation occur by different mechanisms. 58. Gilman, Organic Chemistry, pp. 1637 and Sons (1938). , John Wiley 39. Lucas states that the intermediate, the: mercuric salts are in equilibrium. mercurial and the In addition to this reaction there may be one of irreversible oxidation result ing in a continual decrease in mercuric salt as the reaction proceeds. Thus we can write an equilibrium A Hgc+ /°\ H(j~°AC HC-OAc ^S(OAo)a ■ \0 / ! + h S (Oac)8c \0 / (3) T'*80* j+ c V/ 0 (k) Lucas Intermediate 0H“ G-HgOAc I C-OH V (1 ) Balbiano and coworkers found that all ortho and para propenylan!soles, except isoapiol, react with mercuric acetate to form only mercurous acetate or free mercury and a glycol. On the basis of the latter mechanism, it must be assumed that apiol is unique, in as much as it alone forms a mercurial sufficiently insoluble or stable to cause the reaction to proceed to the right as well as to the left. Thus with Isoapiol a mercurated product and a glycol are formed simultaneously. In all other cases the mercurial is suffi ciently soluble or unstable to establish, equilibrium, condi tions. The equilibrium is therefore forced to the left by the irreversibility of the oxidation— reduction reaction. If this latter explanation is adopted, the oxidation 0Q can be explained on the basis of a modified Criegee mechanism. * For the oxidation of olefins to glycols using hydrogen peroxide with osmium tetroxide as the catalyst, he writes: -C 0. 8 + J-0 3oa -c cr -C-0 | y>aoa _£•£. -c-o -C-OH | + Haoao4 -e-os Modifying this formulation to mercuric or silver acetate, we can w£ite o o / \ H C P /H \ 0 i ° / \H _ G: O s s Cn . 0V P /H v :6:+ C ' | CH0 0 o \ O (m) 0 CHa / \H I . C: Os:CsO:Hg+ I ' 0 " — ► C-O-C V » oh. (o) 59. 60. CH0 0 y \ H .. I ... ?+ \ CsOsCjQRHg 1 V — »■ C-O-G^I ^ e“ s (p) x. 1 (P O;0:+C^" H | CHS (n) ,0 V <rH° / \ H 9 : sCn C 0 CHS H .. I C-0-C=0 1 ■ -0 + H G-O-C^i-CHa v (q) Criegee, Ann. 481, 263 (1930). Organic Chemistry, Karrer (Translation by Mee), p. 51, Hordemann Publishing Company, Inc. (1938). 41. W i t h two mols of mercury a similar procedure could be used to show formation of mercurous mercury in the reaction. The reaction above shows only one molecule of mercury taking part in the reaction. It is quite possible that two mole cules may take part in the reduction of one molecule of di oxene resulting in a three body collision. Indovina and sea Manfroi found that the mercuric chloride oxidation of ascorbic acid; collision. an enediol, actually involves a three body The differences In activity between mercury and silver and the non-reaction of cupric acetate can be explained on the relative ability of the metals to polarize the carbonyl group (as in m ) . The two types of mechanisms are different in that one postulates a carbon to mercury bond while in the other only carbon to oxygen bonds are postulated as Inter mediates . From dioxene the investigation was turned to a study of the more simple vinyl-type ethers. were run on vinyl ether. The first experiments If this ether acts like dioxene towards mercuric acetate, glycollic aldehyde and acetaldehyde or two molecules of glycollic aldehyde would result (see equation (4) ). Experimentally no aldehydes were obtained. When the reaction was carried out at ice temperature very little reaction, besides polymerization, was noted. At room temperature a small quantity of a white crystalline substance, 42. ^CH^CHa 0 + H g (O A c )e + H 20 y GE-CEs 0 GH=GHa Hg HO Ac x CH-CHa i I a OH OH \ Hg (OAc U) H sO + H+ X OH OH I CHa-OE 2 | CHO ch=ch2 I s OH I .CH-CHa 0 \ I OH 'If HC-CHa II 0 CH-CHg i CHa-CHO I OH OH which turned black at 250° but did not melt below 285°, was obtained in addition to considerable quantities of polymerized products. Polymerization might be expected since it is well known that acids and certain metal salts do promote the 68 formation of polymers. Prom these experiments there were some indications that the double bond might reduce mercuric mercury if polymerization could be prevented. Because the experiments with vinyl ether showed little possibility of obtaining additional data on the mercuric acetate oxidation, and because only one aldehyde could be formed by partial reaction, a monovinyl ether. it was decided to investigate The monovinyl ether, it was hoped, would show less tendency to polymerize. The reaction in this case should be: (5) / R 0 Hg (OAc )g ROH + HC-CH-Ri II I 0 OH H*0 'C = C -R t H H Hg' 62. Carothers, Chem. Rev., _8, 394 (1931). 2H0AC A higher boiling ether vinyl ether seemed to be desirable so -ethylvinyl n-butyl ether was selected for the experi ments. Several sets of conditions were used, including (a) shaking the ether with a saturated solution of mercuric acetate, (b) shaking a benzene solution of the ether with aqueous mercuric acetate and (c) dropping a benzene solution on w a r m aqueous mercuric acetate. All of these experiments resulted in a yellow, rubber-like polymer. Although slight indications of reduction of mercurous acetate were observed in the latter experiment, no oxidation products were obtained. In all of the above experiments with @ -ethylvinyl n-butyl ether the solution was acid due to hydrolysis of mercuric acetate. It seemed possible that polymerization was caused by the catalytic effect of the acid. To test this hypothesis an experiment was performed in which the aqueous solution was buffered by the addition of sodium acetate. In spite of the buffer action, however, the usual yellow, gummy polymer was obtained. It is apparent that the polymeriza tion is catalyzed by the salt, and may or may not be cata lyzed by the acidity of the solution. Since polymerization was observed in all these reactions with mercuric acetate, advisable. a change of salt and of conditions seemed The ether was refluxed with silver acetate In benzene solution. After ten minutes a black precipitate was 44. obtained showing reduction of th© silver. products could not b© ascertained* however. The organic By analogy w it h the reaction dioxen© in non—polar media* the equation representing the change is probably: CHs -C H a -C H 3-C H s o ' + n c e = c e - c h 3- c h b G H g-C H a-G H g-C H g 2AgOAc — 0 \jh -C H -C H s-C H s I I OAc OAc The preparation of 0 -ethylvinyl n-butyl ether, used in this work* has not been recorded. formation of the The method involves -chioro ether by passing dry hydrogen chloride into a mixture of butyraldehyde and n-butyl alcohol, drying over calcium chloride, and direct bromination of the chloro ether without isolating it. These reactions were carried on according to the method of Boord and coworkers. 63 ,64 The dibromo ether was then dehalogenated with magnesiummagnesium iodide mixture, using the method of Summerbell and 48 Um h oefer. To investigate the reaction of vinyl ethers with mer curic acetate further, the work of Balbiano and coworkers was continued. As was previously stated in all the anisole compounds that reduced mercury the methoxy group was either ortho or (in most cases) para to the propenyl group. There remained the possibility that the double bond was activated 63. 64. Swallen and Boord, J. Amer. Ghem. S o c ., 52, 651 (1930). Dykstra, Lewis, and Boord, J. Amer. Chem. Soc. 52, 3396 (1930). by the benzene ring. however. Manchot Evidence to the contrary was recorded, had reported that styrene forms a mer curial of composition, 308H 8 -3Hg(0H)Cl*HgCl , and Hesmeyanov 15 and Freidlind styrene. reported two mercurials, (XI) and (XII), from If the reducing power of these compounds is due to the vinyl-type grouping, m-propenylanisole should mercurate. 57 By the principle of vinylogy m-propenylanisole is not a vinyl ether but an allyl ether. Balbiano and coworkers g ^ gg S3 found that allyl ethers mercurate to form two isomers. 9 9 The allyl nature ofm-propenylanisole can be seen by the dia grams below: 0CHo / OCH0 S / V I-CH=GH-CH\ / Eliminating the -CH=CH- group in the benzene ring there is a single bond between carbons 3 and 4 in the first reson ance Isomer, and a single bond remaining between carbon 1 and 4 In the second isomer. To ascertain the correctness of this hypothesis, m-propenylanisole was shaken with an equimolar quantity of mercuric acetate in aqueous solution for twelve days. During this time a solid white precipi tate was formed. An equimolar quantity of aqueous sodium chloride was added and the mixture was shaken overnight. A white solid was filtered from the solution, washed with water, dried. A small portion was soluble In alcohol. and then On remov al of the alcohol a white solid, which did not melt below 250°C, remained* The alcohol insoluble portion did not melt below 235°C but sublimed at 200°G. On a spatula it burned w ith a smoky flame, leaving a black charred residue. On a» nalysis this material was found to contain 63.77 percent mercury. Recrystallization from alcohol yielded a substance whi c h analyzed as follows: carbon, 6.56 percent; mercury, 74.26 percent; and hydrogen, 1.34 percent. This analysis does not correspond to any logical formulation of a simple mercurial. The difference in mercury content indicates that a compound with less mercury, than the recrystallized mater ial, remained in the alcohol solution. Although evidence for the formation of a mercurial is lacking, nevertheless, m-propenylanisole did not give free mercury when it was al lowed to react with mercuric acetate, whereas the ortho and p a r a anisoles did yield free mercury under identical condi tions. The m-allyl compound was reacted In the same manner. Two isomers were obtained, an oil soluble in alcohol and a solid (decomposes 195°C), insoluble in ethanol. As controls o and p-propenylanisoles and methyleugenol and methyliso- eugenol were reacted, with, mercuric acetate under the same conditions. With the two control propenylanisoles and methylisoeugenol free mercury was obtained and the glycols isolated. The otho-glycol boiled at 168-172°C under 7mm. pressure. No attempt was made to separate the isomers, which should exist by analogy with the para glycol. Car bon and Hydrogen analysis showed the compound to be C loH 14!03 , the correct formula for this glycol. With methyleugenol the two Isomeric mercurials were obtained, substantiating the work of Balbiano. In addition to Indicating that the vinyl ether group ing Is necessary for reduction of mercuric acetate, the re sults prove that hydrolysis to a vinyl alcohol structure is not necessary for reduction. In view of the results of this investigation some doubt was cast on the w -ethoxystyrene studies of Manchot. decided, tions. therefore, It was to repeat the work varying his condi To obtain results comparable to those on the ani soles, ^ -ethoxystyrene was shaken with one mol of mercur ic acetate and with two mols of mercuric acetate in two sep arate reactions, and, indeed a mercurial was formed. one mol of mercuric acetate, With and subsequent transformation to the chloride a mercurial was formed which analyzed for CisHiLaOaClaHga. £>u© to the extreme insolubility of this material a molecular weight determination could not be run. This compound may have the structure: HgCl HgCl Xts formation can be postulated as follows: H H C=C-0E+2Hg(0Ac) 2 \ / V H H / ^ - H - C-OE+ I I HgOAOH / H H -C=C-0-Hg-Q-C=C /\ / \ H -C=C-OH HgOAc \ / Hg (O A o )g HgCl \ / If tills reaction were in accord with, the other results ob tained in this investigation free mercury would be the an ticipated product. However, this is probably another case similar to that of isoapiol. The melting pound is 164-166°C although decomposition point ofthe com occurs atthis temperature with the formation of a grey-brown infusible residue. With two mols of mercuric acetate, a compound similar to Manchot* s was obtained. It did not melt below 250°C, but decomposition occurs when the temperature reaches 115°C. Manchot* s analysis led him to propose the C eH lo0 3H g sC l s and the structure: / V / H H ^-C=C-0H*2Hg(0H)Cl formula It is quite possible that this represents one of the stable 13 mercurial intermediates as mentioned by Lucas and coworkers. The structure of this compound would be, therefore: HgCl(OH) OH \ HgCl 0H This might be intermediate to the mercurial: OH f O ‘C I HgCl HgCl I C-OH I OH The structure proposed is in accord with the reactions, as determined by Manchot. One application of the reaction with mercuric acetate is that of structure proof. To ascertain the position of 6e the double bond in phenyldioxene, and to offer more evidence on the structure of this compound, phenyldioxene was reacted w i t h mercuric acetate in aqueous solution. If the structure is such that the phenyl group is attached to one of the dou ble bonded carbon atoms, the following reaction would be an ticipated: y0 / 0 \ CHS I GHg a X > II--GH \ / 0 Actually, 63. H s° C H s-OH + Hg (OAc )2 — >■ Hg * I + C H sOH / Y 0-0110 I \/ the material reduces mercuric acetate, but no os- W i l liam Smedley, Master of Science Thesis, Northwest ern University (1940). azone was obtained when phenylhydrazine was reacted with the organic products of the reaction. This experiment will be repeated to ascertain the organic products. A dioxadiene mercurial was reported by Umhoefer and Summerbell. This work was repeated and substantiated. Reaction of the dimercurial with iodine in potassium iodide solution resulted in an iodine-containing oil, soluble in ether. The material decomposed to give free iodine and a tarry residue when isolation was attempted. EXPERIMENTAL A. Reactions of Dioxene 1. Preparation of Dioxene: Dioxene was prepared according to the method of Sum45 merbell and TJmhoefer , from 2,3-dichlorodioxene using magnesium-magnesium iodide mixture in dry ether. The yields varied between 40 and 47 percent. 2. Reaction of Dioxene and Mercuric Acetate (mol for mol) in Water. To the dioxene (1.7329 g, .0200 mols) and 10 c.c. of water was added an aqueous solution of mercuric acetate (7*0212 g, .0200 mols In 40 c.c. of Water). precipitate began forming immediately. shaken for one-half hour. A grey-black The mixture was The solid formed In the reac tion was removed by filtration through a previously weighed G-ooch crucible. w i t h water, After washing the precipitated mercury alcohol, and finally ether, the Gooch crucible was placed in a vacuum dessicator over calcium chloride overnight, and then weighed. The mercury weighed 3.361 g. corresponding to 95.98 percent of theoretical. The aqueous filtrate from above was made up to 100 ml. In a standard flask and aliquot portions were used for analysis. To 25 ml. of the solxition was added 1.5 c.c. of phenyl- hydrazine in 15 c.c* of water and sufficient acetic acid to dissolve the hydrazine. ly, Hie mixture was warmed slight allowed to stand for thirty minutes, ed in an ice hath. and then was cool The glyoxal osazone was filtered on a G-ooch crucihle, taken up in ethanol and then crystallized from an alcohol—water solution. Weight of recrystallized material was 1.148 g. (96.40 percent of theoretical, m.p. 161-164®). After several recrystallizations from alcohol- water and finally carbon tetrachloride, yellow crystalline plates, melting at 167-168°C (uncorr.) with slight decom position, were obtained. ss (d.). The literature records 169-17G°C The semicarbazone of glyoxal was prepared from another aliquot portion according to the directions given by Schries ner and Fuson . After two recrystallizations from alcoholwater, the semicarbazone melted at 269-270°C ( c o m ) . 66 literature records 270°C (corr.). The The dibenzoate of ethylene glycol was prepared by shak ing 1 c.c. of benzoyl chloride with a 25 ml. aliquot of the filtrate, adding 5 c.c. of 20 percent sodium hydroxide so lution in portions so that the solution was kept slightly alkaline at all times. 65. 66. The precipitate was filtered, wash- Fischer, Ber., 17, 575 (1884). R. L. Schriner and R. G. Fuson, The Systematic Identi fication of Organic Compounds, John Wiley and Sons Inc. (1935), page 145, procedure A. e& with, dilute alkali and then with water. The precipitate weighed 1.179 g., corresponding to 87.26$ yield. After re crystallization from alcohol-water solution the dibenzoate melted at 72.3— 73*0°0 (uncorr•)« Gabriel and Heymann re corded 73-74° (corr.). In another experiment in water 96.4 percent of theo retical mercury was obtained. 3. Reaction of Dioxene and Mercuric Acetate (One Mol of Dioxene to Two Mols of Salt) in Water. To dioxene (1.5098 g., .0176 mols) was added 11.184 g. (.0352 mols) of mercuric acetate In 50 c.c. of water. A white mother-of-pearl-like precipitate began to form im mediately with evolution of heat. The reaction mixture was shaken for one-half hour and filtered through a Gooch cru cible. The precipitate was washed with 5 c.c. of water, followed by alcohol and then ether, vacuum dessicator. and then dried in a The mercurous acetate, precipitated, weighed 8.889 g. corresponding to a 98.29 percent yield. The solubility of mercurous acetate in water is appreci able, accounting for the divergence from theoretical. It was found that mercuric or mercurous ions In the aqueous solution interfered In the preparation of glyoxal osazone. 67. The filtrate was, therefore, reacted with hydro- Gabriel and Heymann, Ber., 25, 2498 (1890). gen sulfide, and the precipitated mercury sulfides removed from solution. The solution, after removal of mercury salts, was made up to 100 ml*, and 18.75 ml. were taken for preparation of the glyoxal osazone. The same procedure as in part 2 gave .8000 g. of glyoxal osazone (98.78 percent of theoretical) which, after recrystallization from ethanol-water mixture and then carbon tetrachloride, melted at 168°G. The ethylene glycol dibenzoate melted at 71-72°C. after two recrystallizations from ethanol-water mixtures. To test the possibility of the 2,3-di acetate of dioxane as the possible intermediate, the 2,3-diacetyldioxanb (1 g.) was added to 35 c.c. of water. goes into solution Immediately, Most of the acetate and the rest slowly. Af ter shaking for ten minutes, phenyl hydrazine (1.5 g.), in 7 c.c. of water and enough acetic acid to obtain a clear solution, was added. The yellow precipitate of the osa zone formed immediately. 4. Reactions of Dioxene and Mercuric Acetate in Meth anol. To dioxene (3.3 g., .038 mols) In 100 c.c. of abso lute methanol was added mercuric acetate (25.0 g., .078 mols). A white precipitate of mercurous acetate began forming immediately. The mixture was shaken for one-half hour. At the end of this time the precipitate was filter ed, washed with dry methanol, cator. and dried In a vacuum dessi- The weight of precipitate was 19.6 g. or 96.2 per cent of theoretical. In a second reaction in methanol, dioxene (4.8 g., .056 mols) wage added to 10 c.c. of methanol, dried over anhydrous MgSO^. Then mercuric acetate (17.8 g., .056 mols), suspended in 50 c.c. of anhydrous methanol, was added in small portions. mediately. A grey-black precipitate began forming im After standing for thirty minutes, tate was filtered. overnight, the precipi The precipitate was allowed to stand and the globule of mercury that coagulated in the bottom was removed, washed; and dried with absorbent pa per. The mercury weighed 10.4 g. (92.8 percent of theoret ical). Some of the precipitate, which remained in the fil ter paper, was probably finely divided mercury. An unsuc cessful attempt was then made to determine the organic con stituents in the methanol solution, by vacuum distillation of the residue after removal of the methanol. Separation of the products by addition of water seemed inadvisable, be cause of the possibility of hydrolysing the product. 5. Reactions of Dioxene and Mercuric Acetate In Benzene. In a test run equimolar quantities (approximately .05 mol) of dioxene and mercuric acetate were placed In a round bot- tom flask with 25 c.c, of dry benzene (dried over calcium chloride). The reaction mixture was shaken for two days at room temperature. At the end of this time no evidence of reaction was apparent, for six hours. so the mixture was heated under reflux At the end of this time a black precipitate of mercury was obtained. Two runs were made by refluxing a benzene solution of dioxene with an equimolar quantity of mercuric acetate. Since they were quite similar only one will be described. Dioxene (9.920 g., acetate (36.97 g., .116 mols) was reacted with mercuric .116 mols) in dry benzene (75 c.c.). The mercuric acetate used in the reaction was previously dried In a vacuum dessicator. The reaction was carried out In a 200 c.c. round bottom flask fitted with a reflux condenser. The condenser was fitted with a soda-lime drying tube to exclude any moisture. gently for two days. The reaction mixture was refluxed At the end of this time the precipitate which was grey-black in color, was removed by filtration, the benzene was removed by distillation. and Approximately 10 c.c. of a liquid, which smelled strongly of acetic acid, remained in the flask. Vacuum fractionation of the liquid gave a small portion distilling at 158°C under 25mm. pressure Attempts to cause the material to crystallize were fruitless. The fraction was almost Insoluble in water, but when boiled with water it hydrolysed readily. The hydrolysate was acid 57. to litmus. Addition of phenylhydrazine in dilute acetic acid gave a slight crystalline precipitate* too small to recrystallize. The derivative melted about 160°G Melting point of glyoxal osazone 169-170°C (d). (d). The pre cipitate filtered from the reaction mixture contained con siderable quantities of white material* presumably mercurous acetate* along with the dark grey precipitate, obtained when mercury is precipitated in these reactions. 6. Reaction of Dioxene and Mercuric Acetate without Solvent,. To dioxene (8.421 g., .0976 mols) was added 31.18 g. (.0976 mols) of mercuric acetate. ten minutes* after which a reaction* able heat* was noted. darken. There was a lag of about accompanied by consider The white mercuric acetate began to After shaking the reaction mixture overnight an additional 10 c.c. of dioxene was added. The mixture was then shaken for one week and then allowed to stand for one week. The precipitate* grey-black in color, was filtered from the solution and washed with ether. It weighed 20.78 g. (theoretical weight 19.59 g . ) after drying. Apparently some mercurous acetate was not reduced to free mercury. The ether and dioxene was removed by distillation at atmospheric pressure* and the residue* which had a strong acetic acid odor* was distilled under reduced pressure. A 2.13 g. fraction boiling at 110-130°C under 9 mm. pressure was collected. This material was dissolved in about 10 c.c. of water and allowed to stand in an ice ba.th overnight• needles crystallized from the solution* Long white The crystals were washed with ice water, dried in a vacuum dessicator, weighed (.10 g. obtained). to be 105.5°C (softening, and The melting point was determined appeared at 105°C). A mixed melt ing point with the diacetate of dioxane, prepared from 2,36© dichlorodioxane and sodium acetate in glacial acetic acid, showed no depression. Yield of di acetate .50 percent. The major portion of the residue after removal of ether and dioxene was left as tar. Only a small portion could be dis tilled. 7. Reactions of Silver Acetate and Dioxene Dioxene (1,923 g*, .0223 mols) was added to 7.48 g. (.0446 mols) of silver acetate and 21 c.c. of water. The mixture was shaken for four days, after which the precipi tated material was filtered and weighed. tate 5.624 g. Weight of precipi (Theoretical 4.76 g.). The filtrate was made up to 200 c.c.^and 100 c.c. were taken for analysis. The excess silver was removed by precipitation as the sulfide and the glyoxal formed was determined as the osazone. 14.9 percent of theoretical. Weight of osazone .385 g. or The melting point of the crude material was 161-163°C. Several other experiments with aqueous silver acetate substantiated the findings in this experiment, i.e., that 68. Boeseken, Tellegen and Henriquez, 55, 1284 (1933). J. Amer. Chem. Soc. the reaction proceeds, but at a much slower rate than with mercuric ac e t a t e . To dioxene (approximately *05 mols) in 50 ml. dry benzene was added anhydrous silver acetate (approximately .1 mol). The mixture was shaken Tor two days without any evidence of reaction. hours. The reaction mixture was then reTluxed Tor six A silver mirror and a precipitate oT silver was Tormed but the organic products were not ascertained. Tollen*s reagent was prepared according to the method 66 oT Shriner and Fuson, page 35, and a small quantity oT di oxene added to the reagent. 8. The test was negative. Reactions oT Cupric Acetate and Dioxene. Two experiments, using two mols oT cupric acetate and one mol oT cupric acetate per mol oT dioxene, respectively, were run in aqueous solution. The mixture was shaken Tor two weeks but no indications oT reaction were observed. B. Reactions with Vinyl Ether. The vinyl ether used boiled at 27-28°C. ether (4.1 g . , .059 mols) 32.0 g. and 15 c.c. oT water was added (.118 mols) oT mercuric acetate in 120 c.c. oT water in small portions. bath. To the vinyl The reaction mixture was kept in an ice A slight grey-black precipitate was noted aTter thirty minutes standing, but the main prodiict was a white polymer. In another attempt vinyl ether (6.384 g., .0913 mols) was added dropwise to 58.17 g. (.1825 mols) oT mercuric 60. acetate in 250 ml. of water. ately Ho precipitate formed immedi in tiie case of dioxene, tut after standing over** night a small amount of a white flaky material was formed in addition to a polymer. mercurous acetate. The white material looked like It did not melt below 285°C, although it darkened at about 250°C. C. Reactions with ^ -Ethylvinyl n-Butyl Ether. 1. Preparation of the Ether. The preparation of this ether involved preparation of <*. -chlorobutyl ether, bromination of the chloroether to 0 -dibromobutyl ether, vinyl n-butyl ether. , and finally debromination to £ -ethylThe first two steps were carried on 60,64 according to the method of Boord and coworkers, and the last step according to the method that Summerbell and 40 Umhoefer reported for the preparation of dioxene from 2,3dichlorodioxane. The butyr aldehyde (72.0 c.c., added to the alcohol (75 c.c., by an ice bath. .75 mols) was .75 mols) in a flask cooled The mixture was transferred to a 500 c.c. separatory funnel, partially submerged In an Ice bath, and dry hydrogen chloride was passed into the mixture for six hours. Towards the end of the reaction the absorption of the gas was very slow. The mixture was allowed to stand In the ice bath for one-half hour and then the lower (water) layer was removed. The upper layer was transferred to a 500 c.c. Erlenmeyer flask, anhydrous calcium chloride was added, and the hydrogen chloride was removed under reduced pressure. The ** -chloroether was dried overnight by contact with cal cium chloride. The ether was kept in a refrigerator, be cause considerable decomposition occurs at room temperature. The intermediate “^-chloroether was not isolated. To the crude product was added the theoretical amount of bromine (120 g., *75 mols) in small portions. The reaction was carried out at ice temperature in a three neck flask, fitted with a mercury seal. complete, After the addition of bromine was the mixture was stirred for one-half hour at ice temperature and then for one-half hour at room temperature. The hydrogen chloride dissolved in the mixture was removed under reduced pressure, ated. and the residue was vacuum fraction The main portion of the mixture (142.1 g.) distilled between 117 and 119°C under 19 mm. Yield of ** , f -dibromo butyl ether 61.5 percent of theoretical. The next step Involved debromination of the ether. To 14.6 g. (.60 mols) of magnesium and 100 c.c. of Grignard ether was added 15 g. (.12 mols) of Iodine in 100 c.c. of Grignard ether. The addition was made slowly so that the color of the solution was never darker than lemon yellow. After all the iodine was added the mixture was stirred until It became white. Then 61.4 g. (.2 mols) of the dibromo- ether, dissolved in 50 c.c. of dry ether, was added dropwise. The reaction is exothermic so the addition was made at such a rate that the ether refluxed gently. was complete, After the addition the mixture was refluxed for one-half hour, and then poured into 400 c.c. of ice water. The ether layer was separated and dried overnight by contact with anhydrous calcium chloride. The ether was removed by distillation on a steam cone and the residue was vacuum fractionated. The 0 -ethylvinyl n-butyl (b.p. 70-85°/83mm.) ether was collected as a clear liquid. The product decolorized a bromine carbon - tetrachloride solution rapidly without evolution of any hydrogen bromide. 2. Reaction with Mercuric Acetate in Water and Methanol. The ether (3.02 g., (.024 mols) of mercuric .024 mols) was added to 7.52 g. acetate in 35 c.c. of water. mixture was shaken for one hour. At the end of this time a yellov/, gummy precipitate was observed. then refluxed for eight hours. The The mixture was In the reaction mixture a few mother-of-pearl-like crystals, resembling mercurous acetate, were observed. Continued refluxing did not cause any mercury precipitation. No precipitation of a hydrazone was observed when the solution, freed of mercury by hydrogen sulfide precipitation, was tested with phenylhydrazine. A polymer was obtained when dry methanol was substituted for water as the solvent. A similar gummy, yellow, polymerized product was obtained 63. w hen 1*6 g. (.012 mols) of the ether was added to 3.8 g. (.012 mols) of mercuric acetate in 20 c.c. of water buffered with 5.0 g. (*06 mols) of sodium acetate. In a test run @ — ethylvinyl ether was dropped onto a hot solution of aqueous mercuric acetate In a three—neck flask fitted with a dropping funnel, mercury seal stirrer and a reflux condenser. during the addition. The mixture was stirred rapidly The resulting mixture was refluxed for ten hours and then was allowed to stand for two weeks. The same yellow polymer was obtained. The solution, removal of the mercury salts, was tested with after p -nitro- phenylhydrazine, but no hydrazone was obtained. 3. Reaction with Silver Acetate in Benzene To 4.0 g. (.031 mols) of the ethylvinyl butyl ether was added 10.3 g. (.062 mols) of silver acetate and 25 c.c. of benzene. The mixture was refluxed for 10 hours. Removal of precipitate, black in color due to reduction of silver acetate to silver, and the benzene left an oily material. No definite products were obtained on distillation. D. Reaction with o-Propenylanisole. 1. Preparation of o-Propenylanisole. This compound was prepared from o-methoxybenzaldehyde (b.p. 123-125° at 17-21 mm. pressure) material. as the starting The aldehyde was converted to 1-(o-anisyl)-1-pro panol, 70 and the alcohol was dehydrated to the propenylanisole. 70. Hill and Hofmann, Ber. 37, 4188 (1904); ibid. 38, 1677 (1905). To 6.1 g. (.25 mols) or magnesium and 10 c.c. of Grig n a r d ether in a 200 c.c. three neck flask, fitted with a re flux condenser, a mercury seal stirrer and a dropping funnel, was added 27.25 g. of ether* (.025 mols) of ethyl "bromide in 50 c.c. The rate of addition was such that the ether re fluxed gently* After the addition was complete, the mixture was refluxed gently for fifteen minutes. The mixture was cooled and 26.7 g. (.197 mols) of o-methoxybenzaldehyde in 50 c.c. of ether was added dropwise with rapid stirring. The mixture was allowed to stand overnight, and then was de composed in ice water and ammonium chloride. The ether layer was separated and dried over anhydrous magnesium sul fate* The ether was removed, leaving the crude l-(o-anisyl) -1-propanol. The crude alcohol was dehydrated by vacuum distillation in the presence of a few crystals of iodine. Three fractions were collected. 21 Fraction Temperature Pressure (mm.) 1 64-65° 1.5 1*5581 2 65-84° 5.3 1.5582 3 84-85.5° 4.5 1.5585 Redistillation of these fractions gave 8.5 g. of o—propenylanisole boiling at 113—116°C under 19 mm. pressure (hD ps *LSi 1.5612, U D 1.5590). The literature records the fol lowing constants for this compound; b.p. 222— 223°C (atmos— 65 , _ 70 SO pheric pressure); Mp 2. 71 1.5604, Reaction of o-Propenylanisole with. Mercuric Acetate and Silver Acetate. To 16.77 g. 7.80 g. (.0526 mols) of mercuric acetate were added (.0526 mols) of o-propenylanisole. shaken for two weeks. after two days. The mixture was The formation of mercury was noted At the end of the shaking the precipitate was filtered, washed with ether and dried. Weight of pre cipitated mercury 11.74 g. (Theoretical weight 10.55 g.). The water solution was extracted with ether, and this ether solution was combined with the ether, used for washing the mercury precipitate. The ether solution was dried over anhydrous magnesium sulfate. The ether vsras removed by dis tillation and the residue vacuum fractionated, giving 3,41 g. of l-(o-anisyl) -1,2-propanediol. The material was analyzed for carbon and hydrogen, giving the following: 3.086 mgm. sample gave 2.158 mgms. of water 7.434 mgms. of carbon dioxide Found Hydrogen Carbon 7.82% 7.74% 65.70% 65.92% Silver acetate (1.55 g., (.69 g., .0046 mols) gether for two weeks. Calculated .0092 mols), o-propenylanisole and 10 c.c. of water were shaken to A black precipitate of silver was observed. 71. Gladstone, J. Chem. Soc. 59, 293 (1891). E. Reactions with m- Propenylanisole. 1* Preparation of m-Propenylanisole• The starting material Tor this compound was nitro benzene, Nitrobenzene was brominated according to the 72 method described in Organic Syntheses* The m —bromnitro— benzene was reduced with tin and hydrochloric acid to m-bromanlline, and the aniline diazotized according to the 7& method of Koelsch. The phenol was methylated in the following manner* To 49.0 g. (.282 mols) of m-bromophenol dissolved in 22*5 g* (.57 mols) of NaOH in 200 c.c. of water cooled to 5-10°C, was added 71.6 g. (.57 mols) of methyl sulfate. During this addition the reaction mixture was stirred rapidly. The mixture was stirred and maintained at 5-10°C for one and one half hours. At the end of this time 12.0 g. (.50 mols) of sodium hydroxide in 50 c.c. of water and 35.8 g. (.268 mols) of methyl sulfate were added. The mixture was then refluxed for three-fourths of an hour, cooled, ex tracted with ether and dried over anhydrous magnesium sul fate. The ether was removed and the anisole distilled under vacuum. residue. There was no forerun and only a small amount of Exactly 44.7 g. of m-bromoanisole (B.P. 77.5-78.0°/ 9 mm.) corresponding to an 84.8 percent yield. 72. 73. This method Johnson and Gauerke, Organic Syntheses, VIII, 46 (1928). Koelsch, J. Amer. Chem. Soc., 61, 969 (1939). is a modification of the method of Diels and Bunzl, who reported a 73 percent yieldl* In the next step m-bromsnisole was converted to 1— (m— anisyl)—1-propanol using the Grignard reaction* 5.84 g. ether, To (.240 mols) of magnesium covered with 30 c.c. of dry as rapidly as refluxing would permit. This Grignard reaction was rather sluggish in starting so that innoculation with a small amount of ethylmagnesium iodide was nec essary. After addition of the bromanisole the reaction mixture was refluxed for one-half hour. cooled and 14.5 g. The mixture was (.250 mols) of prop ion aldehyde in 30 c.c. of ether were added dropwise at such a rate that the ether refluxed gently. After the addition was complete the re action mixture was refluxed gently for one-half hour, and then was poured into a mixture of 200 g. of ice and 40 g. of ammonium chloride. The ether layer was removed, and the aqueous solution was extracted twice with ether. The ether layers were combined and dried over anhydrous mag n esi u m sulfate. fractionated. The ether was distilled and the residue The 1 - (m-anisyl)-1-propanol (27.1 g.) dis tilled at 104-105.5°G at 4 mm. pressure. Yield 68.4 per cent of theoretical, based on the weight of m-bromanisole. % This compound has not been reported so the physical con stants were determined. 74. Diels and Bunzl, Ber., 38, 1496 (1905). D e n s i t y : Weight of pyncnometer +water (2Q°C) 2.2896 g. Weight of pyncnometer alone 1.0749 g. Weight of water (20°G) 1.2147 g. Weight of pyncnometer * sample (20°G) 2.3747 g. Weight of pyncnometer 1.0749 g. Weight of sample so D So 1.070 so Refractive Index: &£> 1.5728 1.2998 g. M.R. a Calculated from M.R=21&li. M ns+2 D (observed) 47.68 M.R. (calculated)^ 47.95 Molar Hefractivity: Molecular W e i g h t : Weight of benzene 25.726 g. Weight of sample .6201 g. Freezing point of pure benzene4.180°C F.P. of benzene + sample 5.445° .737° Molecular Weight: 167.4 166.2 (found) (calculated) Analysis: 2.653 mgms. of sample gave 6.973 mgms. of carbon dioxide 1.860 mgms. of water Found: 71.84$ Carbon 7.84$ Hydrogen * Calculated: 72.26$ Carbon 8.50$ Hydrogen Values from Oilman Organic Chemistry, p. 1739 69 • Several attempts at dehydrating this alcohol catalyt ic ally in the presence of iodine or potassium acid sulfate were "unsuccessful. Finally, the method of Suter and co- 7 5 workers was found to give m-propenylanisole from the 1 - (m-anisyl)-1-propanol. The propanol (10 g., .06 mols) was dropped onto 10 c.c. of syrupy phosphoric acid in a small Claisen flask immersed in an oil hath. The oil hath was maintained at 200°C during the addition. at reduced pressure (24 mm.). The system was kept After the addition was complete the oil hath was heated slowly to 235°C. Ether was added to the distillate and then separated from the water. drying the solution over magnesium sulfate, removed and the residue fractionated. After the ether was A fraction (2*13 g.), hoiling at 118-120°C at 19 mm. pressure, was collected as m-propenylanisole. pressure. B.P. (micro method) 224° at 750 mm. 7e Yields 23.8 percent of theoretical. Moureu reported the hoiling point as 226-229°C., as 1.0013 at 0°G. he 1.5530. and the density The refractive index was determined to Using Moureu1s value for the density the molar refractivity was found to he 47.4 (calculated value 45.95). 75. 76. I Suter, Lawson and Smith, J. Amer. Chem. S o c . 61, 164 (1939). Moureu, J. Chem. Soc. 7 0 i , 646 (1896). 2. Reaction of m-Propenylanisole with Aqueous Mercuric Acetate. Mercuric acetate (4.33 g., .014 mols) in 21 c.c. of water was shaken with m-propenylanisole (2.00 g., for two weeks. .014 mols) After eight hours a white precipitate was noted in the reaction mixture. sodium chloride (2.0 g., At the end of two weeks .034 mols) in 10 c.c. of water was added and the reaction mixture was shaken overnight. After standing two days, the white granular precipitate was fil tered from the solution, washed with water and alcohol. After removal of the alcohol a white solid (weight 0.13 g.) remained. This solid did not melt below 250°C. Similarly, alcohol insoluble material did not melt below 235°C., but sublimed at 2 0 0 ° C . mercury. This crude material was analyzed for The sample was digested with fuming nitric acid 77 (Carius method), and the mercuric ion was precipitated as 7S mercuric sulfide. The sulfide was weighed as such. The following data was obtained. 77. 78. Weight of test tube + Weight of test tube Weight of sample sample 4.5121 g. 4.3290 g. .1831 g. G-attermann and Wieland, Laboratory Methods of Organic Chemistry, p. 65. Translation by McCartney, Macmillan and Co., London (1932). Tredwell and Hall, Analytical Chemistry, p. 172, John W iley and Sons, Hew York (1930). Weight of crucible + mercuric sulfide 18.3962 g Weight of crucible 18.2605 g Weight of mercuric sulfide Mercury .1359 g 63.77 percent. An attempt was made to recrystallize this material. Less than .l::g. could be recrystallized from 230 c.c. of alcohol. Analysis of this material gave: 4.324 mgm. sample gave 3.211 mgm. mercury (74.26$) 3.322 mgm. gave: .399 mgm. of water .799 mgm. of carbon dioxide Pound 1.34 percent hydrogen 6.56 percent carbon P. Reactions w ith Anethol, 1 The anethol used was redistilled (B.P. 119-120°C under S3 17 mm. 2. , 1.5618). Reaction of Anethol with Aqueous Mercuric Acetate. The anethol (12.91 14.6 pressure; nj) , 1.5591; n^ g., (6.00 g . , .0404mols), mercuric acetate .0405 mols), and 65 c.c. of water were treated in the same manner as m-propenylanisole. After the mixture was shaken for two weeks, the precipitate was filtered from the solution, and washed with ether. The precipitate weighed 9.42 g. (theoretical weight 8.14 g.). The filtrate J j was extracted with ether and combined with the ether used for washing the precipitated mercury and mercurous acetate* After steam distillation to remove the unused anethol, the glycols were taken up in ether and dried over anhydrous magnesium sulfate* After removal of the ether 4.84 g, of the glycols remained (65.8$ of theoretical yield). This glycol reacted with acetyl chloride to form an oil. 3. Reaction with Aqueous Silver Acetate. A mixture of anethol (1.84 g., acetate (4.14 g., .0248 mols) shaken for two weeks. material darkened. .0124 mols), silver and 20 c.c. of water were During this time the precipitated Weight of precipitated material 3.51 g. (Theoretical weight based on pure silver 2.67 g.). I G. Reaction with Eugenol Methyl Ether. The ether, obtained from Eastman, was vacuum distilled. The fraction boiling between 137 and 138°C. under 19 mm. 30 was used for these experiments, n^ , 1.5328. I Eugenol methyl ether (6.04 g., acetate (10.82 g.* .034 mols) treated in the same way i .034 mols), mercuric and 44 c.c. of water were /as the m-propenylanisole. After the addition of sodium chloride, the mixture was shaken j ! overnight and the precipitate was filtered and dried. | j Weight of total mercurial: 16.2 g. (92.4 percent of theoret ical based on C 14H 16O0H g Cl). The isomeric mercurial was 73. separated "by differential solubility in alcohol. soluble isomer melted at 115-116°C. (softening at 112°C.) and contained 46.84 percent mercury. Clo^iaOsHgCl 47.28 percent.) (Theoretical for After removal of the alcohol solution of the one isomeric mercurial, the other remained as a gummy viscous oil. H. The alcohol isomer Reaction with Isoeugenol Methyl Ether. Isoeugenol methyl ether (5.99 g., acetate (10.72 g., .0346 mols) .0347 mols), mercuric and water (10 c.c.) when treated as before gave 6.08 g. of mercury and mercurous acetate. (Theoretical weight 8.75 g. of mercury). steam distillation 5.34 g. of the After mixed isomeric glycols remained. J. Reactions with <*/ -Ethoxy Styrene. 1. Preparation of i>u-ethoxy styrene. The starting point was cinnamic acid. The acid was 7s brominated according to the method of Ref yield.. cinnamic in 82.9 percent Using the method of this same author, the dibromoadid was converted to ^ -bromostyrene in 55.6 per- j cent yield by reflrixing with 10 percent sodium carbonate. ! Heating the oj -bromostyrene (65 g., .355 mols) with alco holic potassium hydroxide gave 6*19 g. phenylacetylene 79. ( B.P. 4 5 - 5 2 % . /30 mm.) Nef, Ann., 3 0 8 , 267 (1899). (.0606 mols) of and 10.13 g. (.0684 mols) of ^ -ethoxystyrene (B.P. 102~104°C./l6mm.). Yield of phenylacetylene 17.1 percent; yield of ^ -ethoxystyrene 19.5 percent, based on “'-bromostyrene. The phenyl acetylene was converted into ^ -ethoxy styrene (B.P, 105-106.5°C. at 18 mm. pressure) by refluxing with alcoholic potassium hydroxide for ten hours. The yield was 36.6 percent. 2. Mercuration of uj -Ethoxystyrene with Equimolar Quan tity of Mercuric Acetate in Water. To mercuric acetate (7.06 g., .0222 mols) dissolved in 35 c.c. of water was added. (*/-ethoxy styrene (3.28 g., mols). The mixture was treated in the same manner as the other mercurations. Filtration of the reaction mixture gave 3.44 g. of a white solid., insoluble in water, ether. .0221 alcohol and The melting point of the solid is 164-165°C. (d). When heated above this temperature the material decomposes into a grey-brown solid which does not melt below 250°C. Analysis of the white solid gave the following data: 4.757 mgm. sample gave 3.038 mgm. of mercury 4.598 mgm. sample gave: .634 mgms. of water 3.4-86 mgms. of carbon dioxide Calculated for C lQH lsOsH g sCla Pound Mercury 66.21 63.86 C arbon 21.14 20.68 1.33 1.54 Hydrogen The mercurial has a strong odor of phenylacetaldehyde • However, extraction with ether, gave the oil mentioned above. and evaporation of the ether This oil was tested with phenylhydrazine, but no precipitate was obtained. 3. Mercuration of v* -Ethoxystyrene with Two Mols of Mercuric Acetate for Each Mol of the Styrene. The mercuration was carried on as in the previous ex periments. For this experiment 6.81 g. ( - ■ * mols) of w - ethoxy s t yr en e , 29,30 g. ( and 150 c.c. of water are used, were obtained. 115°C. mols) of mercuric acetate and 20.76 g. of product The material softened and decomposed at This is the same material that Manchot obtained (loc. c i t . ). K. Reaction of To 1.97 g. -Phenyl-2-Dioxene with Mercuric Acetate. (.0061 mols) of mercuric acetate in 10 c.c. of water and 1 c.c. of benzene was added 1.00 g. (.0061 mols) of phenyldioxene (Prepared by Mr. William Smedley). mixture was shaken for two days. The At the end of this time, a dark precipitate of mercury was noted. The precipitate was filtered from the solution and Yirashed with ether. solution was extracted with ether. The The combined ether solutions were dried over anhydrous magnesium sulfate. After removal of the ether by distillation a brown oily aresi due was obtained. The residue was dissolved in alcohol and placed in a beaker in a dry ice-acetone cooling mixture. On standing overnight .05 g. of white crystals, M.P. 68-69°C., was obtained. drazme This substance did not react with phenylhy- and was not, therefore, the expected phenylglyoxal• Water was added to the mother liquor until cloudiness was observed. of ethanol. The solution became clear on addition of one drop No precipitate appeared when phenylhydrazine was added. The aqueous solution was treated with hydrogen sulfide and the precipitated sulfides were removed. After boiling to remove the dissolved hydrogen sulfide, the solution was treated with phenylhydrazine, but again no precipitate was obtained. L. Reaction of.Dioxadiene with Mercuric Acetate. To 1.747 g. (.0208 mols) of dioxadiene in 10 c.c. of ethanol were added 11.29 g. (.0416 mols) of mercuric chloride and 10.5 g. (.125 mols) of sodium acetate in 100 c.c. of water. At the end of four hours a heavy white precipitate h a d formed. After standing overnight, the mercurial was removed by filtr action. The mercurial, which weighed 6.15 g. (92.6 percent of theoretical, assuming G^HgOgHggClg as the product) did not melt below 235°C. The mercurial was reacted with 9 g. (.035 mols) of iodine in 60 c.c. of 14.5 percent aqueous potassium iodide soluition. The excess iodine was removed by adding a small amount of sodium thiosulfate solution. The solution was 77. extracted four times with, ether. The combined ether portions were dried over anhydrous sodium sulfate. removed by distillation. The ether was A tarry residue, which gave no ^•®fin,ite products remained. Evidence of the formation of an ether-soluble compound, containing iodine, was obtained, however. During removal of the ether iodine was liberated, for a blue coloration was obtained when moist starch paper was touched to the solution. Note: Microanalyses by Dr. T. S. Maj Jones Chemical Laboratory, University of Chicago, Chicago, Illinois. 78. SUMMARY 1* mercuric 2. Xn contradistinction to dioxadiene, dioxen© reduces acetate* The reaction lias been studied in aqueous solution, metlianol solution, benzene solution and in an excess of dioxene without other solvents. In most of the reactions studied the organic products have been ascertained. 3. The ability of dioxene to reduce mercuric acetate in non—polar solvents indicates that the reducing action is a function of the special type of double bond and not of an intermediate hydrolysis product. 4. Two possible reaction mechanisms have been proposed for the reaction. 5. Silver acetate oxidizes dioxene and several, of the similar compounds studied, although the reaction is consider ably slower than with mercuric acetate. 6. Gupric acetate does not oxidize dioxene. 7. m-Propenylanisole does not reduce mercuric ions to free mercury, whereas the corresponding ortho and para isomers, when treated under the same conditions, do cause reduction of mercuric mercury to the free metal. The differ ence In behavior is attributed to the fact that compounds which reduce mercuric acetate are vinylogues of vinyl ether, whereas the meta compound Is a vinylogue of allyl ether. 8. A new mercury derivative of u/ -ethoxystyrene has Ww4v«rstt ygLlterary been reported and a structure proposed. A structure for another u> -ethoxystyrene mercurial, prepared first by Manchot (loc. cit.) has been suggested. 9. The reducing powers of vinylogous vinyl ether are greatest when the double bond is activated by two vicinal ether linkages or when it is activated hy a benzene ring in addition to an ether linkage. 10* ethers. This reaction is not applicable to all vinyl— type Ethers that (1) are polymerized by the reagent, (2) form unusually stable or insoluble mercurials, or (5) do not retain the aliphatic nature of the double bond, not oxidized by mercuric acetate. are 80. VITA Georg© Herbert Kalb Bom: August 1, 1915, Woodhaven, Long Island, N. Y. Education: Altoona, Pennsylvania High School, 1929-1952* Lehigh. University, 1932-1938. Northwestern University, 1938-1940. Degrees: B.S. in Chemical Engr., 1936, Lehigh University. M.S. in Chemistry, 1938, Lehigh University. Positions Held: H u n t Rankin Research Fellow in Chemistry, L . U . , 1936-1938. University Scholar, N.U., 1939-1940. Publications: Theory of Two Bath Chromium Tanning, with E. R. Theis. J. A. L. C. A . , 33, 120-144 (1938). Societies: Phi Eta Sigma Pi Mu Epsilon Phi Lambda Upsilon Sigma XI American Chemical Society i ERRATA Page ii. Page Page Page Page Page Page Page Page Page Page Page Page Page Page Si Page Page Page Page Lines 14 and 16 read Mercuration. instead of Mercuriation. 2. Formula VXIX insert H on triv alent carbon* 9* Line 22, read Pinene for Pineni# 10• Formula XIV, Add bond to isopropyl group. Ref. 23, read Zent. for Cent. 11. Lines 10 and 11, read eugenol methyl ether for methyleugenol. 12. Line 1, read Isoeugenol methyl ether for me thyII soeugenol • 13. Line 8, insert at end of sentence, after Hofmann degradation. 14. Line 4, read methylenedioxy for ethylenedioxy-. 21. Line 3, add (iso structure). Line 4, read isonitriles for Isonitites. 24. Line 12, replace - b y ,. 26. Line 10, after point insert of the series. Line 15, read atoms for molecules. Line 17, read in the other seriea for in the series. 38. Line 17, read the reaction is based on. 43. Line 6, omit a benzene solution on. 46. Line 24, read eugenol methyl ether for methyleugenol, read isoeugenol methyl ether for methyl!soeugenol. 47. Line 3, read isoeugenol methyl ether for me thyli s oeugenol • 54. LI ne 14, read went for goes. 61. Insert oc before -chloroether. 70. Line 18, read were for was. 79. Line 4, vinylogous vinyl ethers instead of vinylogous vinyl ether.