AN’ INVESTIGATION OF THE UNCATALYZED ALKYLATEON OF PHENOL WETH l-CHLORO-4-METHYL-3-PEN‘TENE Thais fcr rho chmo 55 Ph. D. MECHEGAN' STAYE COLLEGE Charles Roe Wagner 1955 A? " "- LIBRARY Michigan State University AN INVE‘TIGATION OF THE UNCATALYZED ALKYLATION OF PHETOL WITH l-CHLORO-fi-METHYL—j—PEfiTZfiE By Charles Roe Wagner AN ABSTRACT Submitted to the School of Graduate Studies of Michigan State College of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1955 Approved 4M ‘HJ ABSTRACT Bruylants and Dewael1 and later Favorskaya and Fridman2 reported that l-chloro-4-methyl-5-pentene (I) which was the product obtained when dimethylcycIOpropylcarbinol was treated with hydrochloric acid, was converted back to dimethylcyclopropylcarbinol on treatment with base. It appeared that the { ,' -double bond participated in the OH HCl 3; ,5 e --;__ a; eh-=GH CH CH 01 DH} EHCECH 3H2 K2005 5 EH 2 2 5 2 5 I solvolysis reaction. One would conclude that I should be more reac- tive than most primary halides, being a potential source of a ter- tiary carbonium ion. It had previously been shown5 that tertiary halides, or other unusual reactive halides, such as allyl or benzyl halides, alkylate the aromatic nucleus of phenol without the need of the usual Friedel«Crafts type of catalyst. Primary halides (other than allyl or benzyl) do not alkylate phenols without such a catalyst. It was the object of this research, then, to determine whether the primary chloroolefin, l-chloro-h-methyl-j-pentene, was sufficiently reactive to alkylate the nucleus of phenol without a catalyst, and if so, to determine the structure of the product; that is, to deter- mine whether the alkyl group reverted to the dimethylcyCIOprOpyl- carbinyl form. When I was heated with phenol at 150°, hydrOgen chloride was evolved and two isomeric crystalline products were isolated. Neither of these was the expected pfdimethylcycloprOpylcarbinyl phenol. One was an ether, to which the structure 5,5—dimethylhomochroman (II) was assigned. The elemental analysis and infrared and ultra- violet absorption spectra were consistent with this structure. CH3 0H5 II Furthermore, this ether was obtained when an authentic sample of 5-phenoxy-2-methyl—2-pentene, was treated with a few drOps of sul- furic acid. The second crystalline product was an alkylated phenol. A number of structures were considered and the one which was most consistent with the chemical and physical data was l,l-dimethyl-5- tetralol (III). Further work is needed, before this structure assignment can be considered unequivocal. OH CH5 CH5 III When the ether (II) was refluxed with hydrobromic acid and acetic acid, a second crystalline alkylated phenol was obtained. The structure of this compound is not clear but it appears to be alkylated para to the hydroxyl group. Since saturated primary alkyl halides did not evolve hydrOgen chloride when heated with phenol at 150°, it can be concluded that the double bond of I is involved in this reaction, but from the structure of the products, it is likely that the mechanism is quite different from the hydrolysis of I to dimethylcycloprOpyl- carbinol. During the course of these studies, several new compounds were synthesized, mainly for the purposes of comparison with the observed alkylation products. 2-IsOpr0pylchroman was prepared by treating l-(g-hydroxyphenyl)-4-methyl-5—pentanone with zinc dust and sulfuric acid. 5—Phenoxy-2-methyl-2-pcntene was obtained by refluxing a mix- ture of phenol, l-chloro-A—methyl-j-pentene, acetone and potassium carbonate. The structure of 5-phenoxy—2-methyl—2-pentene was proved by degradation to known compounds. l-(ngethoxyphenyl)-4—methyl-5-pentanone was prepared by the catalytic reduction of the known compound, 2-methoxystyryl isOpropyl ketone. Reduction of l-(gfmethoxyphenyl)-4~methyl-5—pentanone with lithium aluminum hydride gave l-(gfmethoxyphenyl)-4—methyl-5-pentanol. l-(peMethoxyphenyl)-4-mcthyl-5-pentanone was prepared by the catalytic reduction of the known compound pfmethoxystyryl isOprOpyl ketone. Reduction of l-(p-methoxyphenyl)-4-methyl-§-pentanone with lithium aluminum hydride gave 1-(pfmethoxyphenyl)-4—mcthyl-5-pentanol. Derivatives of the new kctones and alcohols were made. DimethylcycloprOpylcarbinylbenzene was prepared by the follow- ing series of reactions. Reduction of the known compound, ethyl 2-carbethoxy-5-methyl-5-phenylbutanoate, with lithium aluminum hydride gave 2-hydroxymethyl-5-methyl-5~phenyl-l-butanol. Treat- ment of the diol with phosphorus tribromide gave 2-bromomethyl-5-methy1'5' phenyl-l-bromobutane. Ring closure with zinc dust gave dimethyl- cyclOprOpylcarbinylbenzene. ErButyl phenyl ether prepared from phenol and isobutylene, was split readily in benzene solution at 500 with hydrosen chloride. Cleavage, rather than rearrangement products were obtained. REFERENCES Bruylants and A. Dewael, Bull. Sci. Acad., Belg., (v), 1 P. _1__l_&, 140 (1928). 2 T. A. Favorskaya and Sh. A. Fridman, J. Gen. Chem., (U.S.S.R.), _1_§, 1421 (1945); c. A. iq, 4655 (1946). 5 J. H. Simone and H. Iisrt, J. Am. Chem. Soc., _§_’_), 1509 (1944). AN INVESTIGATION OF THE UNCATALYZED ALKYLATION 0F PHENOL WITH l-CHLORO-h—METHYL—5-PENTENE By Charles Roe Wagner A THESIS Submitted to the School of Graduate Studies of Michigan State College of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1955 IQLHCEBEII ‘7 L‘o 10. ll. Iv L" D5 *3 v: ’5 Infrared Absorption Spectrum 0; Dimethylcyclopro- pylcarbinOl.........o.......... Infrared Absorption Spectrum of l-Chloro-h—methyl- 5"?611‘0‘3116.ooeeeeoeeoeooeoeoooe Infrared Absorption Spectrum of Neutral Product "A" in Carbon Tetrachloride Solution. . . . . . . . . . Ultraviolet Absorption Spectrum of Neutral Product. . Ultraviolet Absorption Spectrum of a-IsOprOpylchroman Ultraviolet Absorption Spectra of Phenolic Products . Infrared Absorption Spectrum of "3" fide. o O O O I O O O O O O O O O O I O O O O O O O in Carbon Disul- Infrared Absorption Spectrum of "B" in Carbon Tetra- chloride. . . . . . Infrared Absorption Saectrum of Dimethvlcyclopropyl- carbiny1bellzerleoeooeeoeoeeoeeeoee the Methyl Ether of Infrared Absorption Spectrum of “B" O O C O C O O O O O O O O O O O O O O O O I O . Infrared Absorption fide. . . . . . . Infrared Absorption Chloride. e e o 0 Spectrum of Spectrum of I. n" U I. n" U in Carbon Disul- in Carbon Tetra- TABLE OF COHTZKTS PAEE ILTRODUCTION AID HISTORICAL . . . . . . . . . . . . . . . . . l EKPERIVEKTAL . . . . . . . . . . . . . . . . . . . . . . . . 10 Experiments Concerning fieutral Product "A" . . . . . . . 21 Experiments Concerning Phenolic Product "b". . . . . . . 54 DISCUSSICK . . . . . . . . . . . . . . . . . . . . . . . . . 58 SUICIJIARY...........................94 BIBLIOGRA:I:E‘f O O O O O O O O O O O O O O O O O 0 O O O O O O {)6 ACKN OWL EDGl-f EN T The author is deeply indebted to Dr. Harold Hart for his con- stantly valuable guidance and aid throughout this investigation. Also, the writer is appreciative to his wife, Dorothy, for her moral support and able assistance in this work. INTRODUCTION AND HISTORICAL It has long been known that the reactivity of a functional group in an organic molecule is influenced by other groups in its immediate environment. In particular, a functional group on a carbon atom adja- cent to a moiety which is undergoing chemical reaction may influence both the rate at which the process occurs, and its stereochemical course. This phenomenon, known as neighboring group participation, was first investigated in a systematic way with particular reference to displacement reactions by Winstein and his co-workers (1). The normal stereochemical result of a bimolecular displacement process is inversion at the carbon holding the displaced group. Retention of configuration often occurs, however, in the course of a displacement reaction in which participation is possible. Thus, the acetolysis of 35523 2-acetoxycyclohexyl‘p-toluenesulfonats pro- ceeds with retention of configuration (1). The retention of con- figuration is ascribed to the participation of the trans 2-acetoxy OTs OAc l OAc OAc group on the reverse side of 01 as the p—toluenesulfonate group ion- izes. This gives one inversion at CI. The second inversion at 01’ which produces overall retention of configuration, occurs as the entering acetate ion attacks 01 from the opposite side of the parti- cipating group. 2. Isomerization through participation is also possible. Cram (2) studied in detail the acetolysis of the p-toluenesulfonato of 5-phenyl-2-pentanol, which gave a mixture of 5-phenyl-2-acetoxy- pentane and 2-phenyl-5-scetoxypentane. The isomerizstion occurs by + / \l —+ 2 ChipHCHCHZCHg CH3CHCHCHZCH5 I} 0 ‘(//,/’ Ts CHjCHCdCHZCHj and CH50HCHCHZCH§ OAc Ac participation of the phenyl group with 02 as the p-toluenesulfonate group ionizes, followed by attack of acetate at 02 or 05. The concept of participation is not restricted only to stereo- chemical control of a reaction path; a neighboring group also influences the rate of a chemical reaction. Thus, the scetolysis of Eggng 2-iodocyclohexy1‘pfbromobenzenesulfonate is 1800 times the rate for cyclohexyl pfbromobenzenesulfonate itself (5). In general Winstein and Grunwsld (5) observed that the 35523 2-substituted cyclohexyl pfbromobenzenesulfonates react faster than the correspond- ing 23: isomers. This can be attributed to the favorable position of a 25523 substituent, which may participate by a back-side attack during the ionization at an adjacent carbon. In the gig isomer, however, a substituent is not favorably located for participation in this manner, and consequently it is less reactive. 5. Non-functional groups such as the phenyl (2), the carbon double bond (h), and carbon and hydrOgen atoms (5) may also participate in organic displacements. The i-steroid rearrangement in the cholesteryl system involves double bond participation in which all three aspects of neighboring groups are exemplified; i.e., stereochemical control, isomerization, and influence on reaction rate. Shappee (4) has reviewed the 27 steroid rearrangement, which can best be discussed with the aid of the following flow sheet. H\ XI I II OH OH 5 KOAc al. AcOH H"" | ' OCH 5 III The reaction of cholesterol (I) with thionyl chloride or phosphorus pentachloride leads to cholesteryl chloride (II; x equals 01) with retention of configuration at 05. Treatment of cholesteryl chloride (II; X equals 01) with methyl alcohol and potassium acetate forms the methyl ether of ircholestanol (III) in which the configuration at C5 is inverted. The methyl ether of i-cholestanol is unstable 4. in the presence of acid and rearranges to the methyl ether of chole- sterol (11; X equals OCH3); the potassium acetate apparently acts as a buffer preventing rearrangement of the initial product. The reverse reaction, from the methyl ether of ircholestanol (III) to cholesteryl chloride (II; X equals 01), leads to a second inversion at 05, giving the original configuration. A mechanism (4) which satisfactorily explains the retention of configuration at C5 involves the back—side participation of the‘Tv- electrons from the double bond as ionization occurs. This leads to one inversion at 05 when the intermediate ion (V) is formed. The II VI or "" (I) H \\\ if‘l .+ + IVA IVB attacking nucleophilic group would then enter on the opposite side from the participating TH'-electrons, consequently leading to a second 5. inversion and overall retention of configuration at C On the other 5. hand, the entering group may attack 06, whereupon the i-cholestanol system would be obtained. When i—cholestanyl compounds are subjected to ionizing condi- tions, rearrangement to the cholesteryl system occurs. The 05-05 distance in cholesterol is 2.5 A., and in ircholestanol it must approach bonding distance, or approximately 1.5 A., which involves considerable strain; hence, a driving force in the opposite direc- tion from IVA to IVB should exist. An alternative mechanism, referred to as SNZ', for the ifsteroid rearrangement can be pictured as a simultaneous attack of Y"at C6, a shift of the double bond to the 5-5 position, with expulsion of X“. This mechanism has been tentatively ruled out by Winstein and Adams (5). Their argument is based on the fact that the rate of acetolysis "4—9 of cholesteryl p—toluenesulfonate in acetic acid is not affected by potassium acetate except for salt effects. If an 5N2. mechanism were operative, the rate of acetolysis should have been dependent upon the concentration of potassium acetate. The cholesteryl system also shows an increase in chemical reacti- vity due to participation of a double bond. Winstein and Adams (5) studied 6. the acetolysis of cholesteryl Retoluenesulfonate (II; X equals T30) .and cyclohexyl p—toluenesulfonate. The former was found to react at a rate approximately one hundred times the latter. The reaction was kinetically first order in the tosylate and essentially indepenr dent of acetate ion concentration; therefore, the rate controlling step must have been the ionization of the tosylate. The increased reactivity in the cholesteryl system is ascribed to the participation of the unshared electron pair from the 05-06 double bond which would furnish a driving force not possible in the cyclohexyl system. It was of interest to examine the literature for analOgs of the .i-steroid rearrangement in simple acyclic systems. Bruylants and Dewael (7) and later Favorskaya and Fridman (8) reported that l- chloro-h-methyl-5-pentene (VIII) is the product obtained from dimethyl- cyclopropylcarbinol (VII) and hydrochloric acid. This is not too unusual, for if one considers the cycloPrOpane ring as having pro- perties similar to the carbon - carbon double bond, then this is simply an extension of ordinary allylic rearrangements to the cyclo- propane system. It is similar to the conversion of the methyl ether of 9H HCl -———-———45 .._______. _ CH5.?-cg:c§2 aq. K2005 (CH5)ZC—CHCH20H201 0H5 032 VII VIII :1 ifcholestanol (III) to cholesteryl chloride (II; X equals 01) in the presence of hydrochloric acid. What is more surprising, is the conver— sion of the chloroolefin back to dhmethylcyclopropylcarbinol on 7. treatment with base. This is an acyclic analog of the i-steroid rearrangement, but because of the greater flexibility of the system, the double bond need not be fixed in a position favorable for parti- cipation. Possibly the driving force is the Opportunity of ferming a tertiary carboniwm ion. If the double bond in l-chloro-kfmethyl-i-pentene does indeed participate in the solvolysis reaction, then this compound should be more reactive than most primary halides. It has been shown (9) that tertiary halides, or other halides which are unusually reactive, such as those of the allyl or benzyl type, can alkylate the aromatic nucleus of phenol without need for the usual Friedel-Crafts type catalyst. Primary alkyl halides (other than allyl or benzyl) do not alkylate phenols without a catalyst. It was the object of this research, then, to determine whether the primary chloroolefin, l- chloro-hdmethyl-fi-pentene, would alkylate the nucleus of phenols without a catalyst, and if so, to establish the nature of the pro- ducts; that is, to determine whether the chloroolefin reverted to the dimethylcycIOpropylcarbinyl derivative. In this latter connection, it is important to note that often the cyc10propylcarbinyl and cyclobutyl systems are interconvertible. + c c c—— c-—— .4’ \\\ / «e———1v /\ / d&———+p C/ / c o g c -——c X IX XI Reactions which involve the cyc10propy1carbinyl ion (X) may yield 8. rearranged products of the structure IX or XI. Roberts and Mazur (10) reported that treatment of cyclobutylamine or cyclopropylcarbinylamine with nitrous acid gave approximately identical mixtures of alcohols, consisting of 47% cyclobutanol, #8% cyCIOprOpylcarbinol and 5% allyl- carbinol. They postulated that the interconversion of X and XI occurred with a minimum of energy, because both cyclobutylamine and cyc10pr0pylcarbinylamine gave mixtures with nearly identical amounts of the isomeric alcohols. In a later paper, Roberts and Mazur (11) noted that the three methylene groups in cyclOpropylcarbinylamine achieved some degree of equivalence in the course of the reaction with nitrous acid. This was established using 014. The intermediate ion XII was postulated as a possible explanation for the apparent equivalence of three methylene groups |_ .. + /CH\ CH2---L--9H2 ‘CHé L. _I XII The first part of the present work dealt with attempts to pre- pare dimethylcyCIOpropylcarbinyl chloride from the corresponding alcohol. This would be the tertiary chloride isomeric with the homoallylic chloride, l-chloro-h-methyl-j-pentene. These attempts were unsuccessful. The uncatalyzed reaction of l-chloro-t-methyl-fi-pentene with phenol was then examined, to determine whether aromatic alkylation 9. could be included among those reactions which are facilitated by a homoallylic system. Two crystalline products were obtained from the reaction, and the major body of the thesis is concerned with the determination of their structure. It was heped that the present work would also include kinetic data on the reactions of acyclic homoallylic systems with phenols, but since the reaction took an unexpected course, the major task became one of establishing the identity of the reaction products. EXPERIMENTAL §:Chloro-2-pentanone The procedure in Organic §yntheses (12) was followed. To a solution of 450 ml. of concentrated hydrochloric acid in 525 ml. of water was added 584 g. (5.0 moles) of OC-acetyl-Ef-butyrolactone. The mixture was heated cautiously until the carbon dioxide evolu- tion abated. The mixture was steam distilled until a total of 1.2 l. of distillate was collected. The organic layer was separated and the aqueous layer was extracted with three 150 ml. portions of ether. The combined organic extracts were dried over calcium chlo- ride. The reaction was repeated using 156 ml. of concentrated hydrochloric acid, 158 ml. of water, and 116 g. (0.91 mole) of Of- acetyl-if-butyrolactone. The ether solutions from both runs were combined, the solvent removed, and the residue distilled inggggg. Three hundred and sixty-six grams (75%) of 5-chloro-2-pentanone, b.p. 7o°-72° at 20 mm., was obtained. Methyl Cyclopropyl Ketone The procedure was taken from Organic Syntheses (12). To a solution of 185 g. (4.57 moles) sodium hydroxide in 180 m1. of water in a 2 l. round-bottomed, three-necked flask equipped with a motor- driven iron stirrer, a reflux condenser, and an addition funnel, was added 566 g. (5.04 moles) of 5-chloro-2-pentanone during a twenty minute period. While being stirred, the solution was heated cautiously for one hour. To the refluxing solution was slowly added 575 m1. of water. The solution was refluxed an additional hour, then ll. steam distilled. The distillate was saturated with potassium carbonate and extracted with two 150 ml. portions of ether. The combined ether extracts were dried over calcium chloride. The sol- vent was removed through a 50 cm. glass packed column and the resi» due distilled through a short Vigreux column. Three hundred and sixty-six grams (78%) of methyl cyclopropyl ketone, b.p. 1090-1110, was obtained. A similar experiment using 1.57 moles of 5-chloro-5-pentanone yielded 79.5% of the theoretical amount of methyl cyclOpropyl ketone. DimethylcycloPropylcarbinol Method 1. In a typical preparation, 292 g. (2.06 moles) of methyl iodide in 950 ml. of anhydrous ethyl ether was slowly added to 64 g. (2.5 moles) of magnesium turnings in a 5 l. round-bottomed flask equipped with a Friedrichs condenser, a mercuryhsealed stirrer, and an addition funnel. The resulting solution was refluxed for one-half hour. One hundred and seventy-two grams (2.06 moles) of methyl cyclopropyl ketone dissolved in 550 ml. of anhydrous ethyl ether was added dropwise to the stirred, cooled reaction mixture. The mixture was allowed to stand for 12 hours, then hydrolyzed by pouring into a solution of 214 g. (4.0 moles) of ammonium chloride in 1 1. of water and 400 g. of ice. The other layer was separated and the aqueous layer extracted with three 150 m1. portions of ether. The combined ether extracts were dried over potassium carbonate and the solvent was then removed through a Vigreux column. The residue was distilled through a Claisen head and the fraction boiling from 1150 to 1220 was redistilled under reduced pressure using a Stedman 12. packed column. One hundred and fifty-three grams (74%) of dimethyl- cyclopropylcarbinol, b.p. 51.50-55o at 40 mm., n30 1.4510 was obtained. Volkenburgh gt 3}. (15) report for dimethylcycloprOpylcarbinol, nfio 1.4557. Method a. The modified Grignard method of Swain and Boyles (14) was used in one preparation. To 64.5 g. (2.69 moles) magnesium turnings and 800 m1. of anhydrous ethyl ether, 400 g. (2.5 moles) of bromine was added slowly with stirring. After stirring the mix- ture for 5 hours, 100 g. (1.19 moles) methyl cyc10propyl ketone was added to the stirred mixture. To the reaction was added, drOpwise, 800 m1. of ethyl ether containing 2.28 moles of methyl magnesium iodide. The resulting mixture was hydrolyzed by pouring it into a cold 10% sodium carbonate solution. The ether layer was separated and the aqueous layer extracted with ethyl ether. The combined ether extracts were dried over potassium carbonate, the solvent removed, and the residue distilled. Twenty-one grams (18%) of dimethylcycloprOpylcarbinol, b.p. 119.10-1210, was obtained. Fifty-three milliliters of a dark red residue remained. _Attempted Preparation of Dimethylcyclopropyloarbinyl HydrOgen Tetra- chlorophthalate The general procedure of Fensler and Shriner (15) was followed. To 1.21 g. (0.05 mole) of magnesium turnings, in a 500 m1. round- bottomed flask equipped with a stirrer, condenser, and addition fun- nel was added 4 ml. (0.05 mole) ethyl bromide in 75 m1. of anhydrous ether. Five grams (0.05 mole) of dimethylcyclopropylcarbinol dis- solved in 25 m1. of ether was added, dropwise, to the ethyl l5. magnesium bromide solution. When the evolution of ethane abated 100 ml. of anhydrous dioxane was added. A white precipitate fommed. The temperature of the mixture was increased to 60° and 14.5 g. of tetrachlorophthalic anhydride was added. After stirring for one hour at 50° the contents of the flask were cooled and poured into 625 m1. of 2 N hydrochloric acid and 250 g. of ice. The hydrolyzed mixture was filtered to remove unreacted tetrachlorophthalic acid. The ether layer was separated and washed with water and then extracted with one 100 m1. portion and one 25 m1. portion of 5% sodium hydrox- ide solution. The combined alkaline extracts were acidified with 6 N hydrochloric acid, and the precipitate which formed was removed by filtration. After recrystallization from a mixture of petroleum ether and ethyl other the solid melted with decomposition at 250°. The melting point of tetrachlorphthalic acid is 250° with decomposi- tion. lgphloro—4—methylfi5épentene The procedure of Favorskaya and Fridman (8) was used. Sixty grams (0.5 mole) of dimethylcyclopropylcarbinol was stirred vigor- ously with a solution of 150 ml. of concentrated hydrochloric acid (d. 1.19) and 150 ml. of water for 2.5 hours. The organic layer was separated, washed with 200 ml. of water, and dried over calcium chloride. The crude l-chloro-4~methy1-5—pentene, b.p. 1290-1540, after a simple distillation, was redistilled through a glass-packed column. Forty-nine grams (67.1%) of l-chloro-4-methy1-5-pentene, o b.p. l5l.6°-155°, n35 1.4444, was obtained. Favorskaya and 14. Fridman (8) reported a 76% yield of l-chloro-4qmethy1-5-pentene, b.p. 1510-1550, n$§'5 1.44485. The reaction was repeated several times and the yield of the crude 1-ch1oro-4-methyl-5-pentene, b.p. 1500-1550, varied from 71% to 80% of the theoretical. ‘Rgaction of l-Chloro-4-methyl-5epentene with Aqueous Potassium Carbonate The procedure of Favorskaya and Fridman (8) was followed. Nineteen and four-tenths grams (0.16 mole) of l-chloro—4—methyl-5— pentene was refluxed with 200 ml. of 10% potassium carbonate solu- tion for 9.5 hours. The mixture was refluxed with stirring for an additional six hours. The reaction mixture was cooled and the organic layer separated. The aqueous layer was extracted with three portions of ether. The combined organic extracts were dried over magnesium sulfate. The solvent was distilled through a short_ Vigreux column and the residue distilled in a semi-micro distilla- tion apparatus. Eleven and four-tenths grams (70%) of dimethyl- cyc10pr0py1carbinol was obtained. Favorskaya and Fridman (8) reported a 60 per cent yield of the product. A 2 ml. center cut was taken for the infrared spectrum. The spectrum was identical with that of an authentic sample of dimethylcyclapropylcarbinol. Reaction of Dimethylcyclgpropylcarbinol and Phosphorus Trichloridg The general experimental conditions of Hatch and Nesbitt (16) were used. Ten grams (0.1 mole) of dimethylcyclopropylcarbinol and 2.2 g. (0.028 mole) of pyridine were added over a twenty minute 15. period to a 5.5 g. (0.04 mole) of phosphorus trichloride with cooling. The mixture was allowed to stand at 00 for forty minutes. The mix- ture was washed with two portions of 10% sulfuric acid and four portions of 10% sodium carbonate and dried over sodium sulfate. The material was distilled through a modified Claisen head. Two fractions were collected: fraction 1, b.p. 70°-75°, n20 1.4260, D 0.5 g.; fraction 2, b.p. 119°, nfio 1.4550, 5.0 g. Volkenburgh, '33-31. (15) report for isoprOpenylcyclopropane, b.p. 70.410, n30 1.4254. Fraction 2 was recovered dimethylcyclopropylcarbinol. Reaction of Dimethylcyclopropylcarbinol and Phosphorus Pentachloride The general procedure of Gerrard (17) was followed. A suspen— sion of 10.4 g. (0.05 mole) phosphorus pentachloride in 40 m1. ethyl ether was added slowly to a solution of 51.6 g. (0.4 mole) pyridine and 10 g. (0.1 mole) dimethylcyc10pr0py1carbino1 in 50 ml. of ethyl ether at -lO°. The mixture was allowed to react for sixteen hours at 15° and then filtered. The filtrate was washed with 10% sulfuric acid, then 10% sodium carbonate, and dried over sodium sulphate. The solvent was removed and the residue distilled through a modified Claisen head in 15223. Sixty-one and six-tenths per cent (6.15 g.) of dimethylcyclo- propylcarbinol, b.p. 860 at 145 mm., n30 1.4540, was recovered. The experiment was repeated four times varying the solvent and mode of addition. Dimethylcyclopropylcarbinol or l-chloro-4—methy1- 5-pentene were obtained in these experiments. Reaction of DimethylcycloprOpylcarbinol and Thionyl Chloride The general procedure of Gilman and Harris (18) was followed. 16. A solution of 14.5 g. (0.12 mole) thionyl chloride, 10.5 g. (0.15 mole) of pyridine and 10 m1. chloroform was added slowly at 0° to 10 g. (0.1 mole) dimethylcycloprOpylcarbinol in 10 ml. chloroform. After the addition the mixture was allowed to stand at room tempera- ture for one and one-half hours. The mixture was washed thoroughly with water, dried over potassium carbonate, and then the solvent was removed. The residue was distilled under reduced pressure. Six and eight-tenths grams (58%) 1-chloro-4-methyl-5—pentene, b.p. 52° at 55 mm., n52 1.4440 was obtained. Reaction of 1—Ch1oro-4-methy1:5fpentene and Potassium Acetate The procedure of Bruylants and Dewael (7) was followed. A mix- ture of 16.5 g. (0.169 mole) of potassium acetate, 20 g. (0.169 mole) of 1-chloro-4-methy1-5-pentene, and 2 m1. of acetic acid were refluxed for thirty hours. The cooled mixture was poured into water. The organic layer was separated, dried over potassium carbonate, and distilled. Three and six-tenths grams (15%) of 1-acetoxy-4~methy1- 5~pentene, b.p. 1550-1750, n30 1.4551, was obtained. Bruylants and Dewael (7) reported for l-acetoxy—4—methyl-5-pentene, b.p. 170°- 171°, n30 1.45107. Reaction of 1-Chlorohexane and Phenol at 150° The apparatus described by Bordeaux (19) was used. A mixture 0f 6.05 g. (0.05 mole) of l-chlorohexane and 18.8 g. (0.2 mole) of phenol was heated at 1500 in an oil bath while a stream of dry nitro- gen was bubbled through the mixture. The nitrogen was used to sweep the hydrOgen chloride, which would be formed if alkylation did occur, from the reaction mixture into a potassium carbonate adsorption tube. 17. The reaction was followed by determining the amount of hydrOgen chloride adsorbed by the potassium carbonate at various intervals. (The per cent of the theoretical amount of hydrOgen chloride which would have been evolved, if complete alkylation occurred, was cal- culated and recorded in Table I.) The chloride was determined by the Volhard procedure. The reaction mixture remained clear TABLE 1. Per Cent H01 Evolved 0 0 0 5.0 4547 throughout the heating period. The cooled mixture was dissolved in 20 m1. of benzene, extracted with three 15 ml. portions of 10% sodium hydroxide, and dried over potassium carbonate. The solvent was removed and the residue dis- tilled. Seventy-one per cent (4.28 g.) of l-chlorohexane, b.p. 150°, was recovered. One milliliter of l-chlorohexane remained as hold-up in the distillation apparatus. The alkaline extracts were acidified with acetic acid and extracted with four 20 m1. portions of benzene. The combined ben- zene extracts were dried over sodium sulfate, the solvent removed, and the residue distilled $2.!EEEQ‘ Sixteen grams (85%) of phenol, b.p. 670-70o at 5 mm., was recovered. One and one-half grams of phenol remained as hold-up in the distillation apparatus. Reaction of 1-Chloro-4—methyl-5gpentene and peCresol Twenty-one and two-tenths grams (0.2 mole) of p-cresol and 5.94 18. g. (0.05 mole) l-chloro-4~methyl-5~pentene were placed in the appara- tus described by Bordeaux (19). The mixture was heated at 1500 while nitrOgen was bubbled through it. The hydrOgen chloride was determined as previously described. The mixture became dark after heating for five minutes. TABLE II. Time - Hours 0 1 2 5 41 5 7 9 11 Per Cent H01 Evolved 0 4.1 lLljél 58.5 41.9 50.5 56.1 60.1 The mixture was cooled, dissolved in 50 ml. of benzene, extracted with two 20 m1. portions of 20% sodium hydroxide and 20 m1. of Clai- sen's alkali, and dried over potassium carbonate. The solvent was removed and the residue was distilled in 32322 using a semi-micro distillation apparatus. Two and seven-tenths grams of material, b.p. 850-95o at 1.5 mm., was obtained. A dark residue (2.7 g.) remained. The alkaline extracts were acidified and extracted with three 50 m1. portions of benzene. The combined benzene extracts were dried over sodium sulphate, the solvent removed, and the residue distilled .12 12332 using the semi-micro distillation apparatus. Fourteen and one-tenth grams (66.6%) of pfcresol, b.p. 700-75o at 1.5 mm., was recovered. The residue (2.6 g.) would not distill and when cooled became very hard. The reaction was repeated using 42.4 g. (0.4 mole) of p—cresol and 11.8 g. (0.1 mole) of 1-ch1oro-4-methyl-5-pentene. The mixture was heated thirteen hours at 1500 and treated as described above. Four grams of neutral material, b.p. 900-95o at 1.5 mm., was obtained. 19. The benzene was removed from the alkali soluble material and the residue distilled in 15222. Twenty-five grams (60%) of pfcresol, b.p. 850-86o at 2.0 mm., was recovered. The residue (9.7 g.) would not distill. Reaction of l-Chloro—4-methylj5gpentene and Phenol at 1500 The apparatus described by Bordeaux (19) was used. A mixture of 5.95 g. (0.05 mole) of 1-chloro-4-methyl-5-pentene and 18.8 g. (0.20 mole) of phenol were placed in the reaction flask. The temp- erature for the reaction was 150°. Dry nitrogen was bubbled through the mixture and the amount of hydrOgen chloride evolved determined as previously described. TABLE III. r Time " Home O 1e5 5e 5e 7e 9e lle Per Cent H01 0 21.8 454.6 41.8 46.8 51.6 54.4 The mixture, which had darkened within ten minutes at 150°, was cooled, dissolved in benzene, extracted with 10% sodium hydrox- ide, and dried over sodium sulfate. The solvent was removed and the residue, which was distilled in 33933, gave 2.15 g. of material, b.p. 125°-161° at 5 mm. One-half gram of a dark viscous residue remained. The alkaline extracts were acidified, extracted with benzene and dried over sodium sulfate. The solvent was removed and the resi- due distilled in 33332. Eight and four-tenths gram of phenol, b.p. 640-680 at 5 mm., and 1.6 gs Of material, bop. 790-1510 at 5 m.’ 20. were obtained. One gram of a dark viscous residue remained. The reaction was repeated using 149 g. (1.58 moles) of phenol and 57.5 g. (0.517 mole) of 1-chloro-4-methy1-5-pentene. The mixture was stirred and heated at 1500 for twelve and one-half hours. The mixture was treated as previously described. After the benzene was removed from the neutral portion the residue was distilled in 13223 and the following fractions were obtained: fraction 1, b.p. 80°- 92° at 1 mm., 9 g.; fraction 2, b.p. 92°-116° at 1 mm., 5.5 g.; fraction 5, b.p. 1160-140o at 1 mm., 7.0 g.; fraction 4, b.p. 140°- 1950 at 0.5 mm., 7.5 g. One gram of a dark viscous residue remained. Fraction 1 crystallized at room temperature. After recrystalliza- tion from petroleum ether, fraction 1 melted at 470-480. The remaining fractions were viscous liquids which did not solidify. The benzene was removed from the alkali soluble portion and the residue distilled in 32223. The following fractions were obtained: fraction 1a, b.p. 540-60o at 5 mm., 96.5 g.; fraction 2a b.p. 60°-64° at 2 mm., 6 g.; fraction 5a, b.p. 110°-115° at 2 mm., 16.4 g.; fraction 4a, b.p. 1160-185o at 1.5 mm., 8.0 g. Five grams of a dark residue remained. Fractions la and 2a were recovered phenol. Fraction 5a solidified and after recrystallization from petroleum ether melted at 1150-1140. Fraction 4a was a viscous oil which did not solidify. Fraction 1 will be referred to as compound "A" and fraction 5a will be referred to as compound "B". Ariel} Calcd. for "1", 01211150: 0, 81.77; H, 9.15. Found 0, 81.99: H, 9.10. 1 Analyses were performed by the Clark Microanalytical Labora- tory, Urbana, Illinois. 21. Calcd. for "B", ClZHLSO: C, 81.77; H, 9.15. Found: C, 81.75; H, 9e52s Experiments Concerning Neutral Product "A" Attempted Thermal Rearrangement of the Neutral Product "A" Four and one-tenths grams of "A" was placed in a 50 m1. round- bottomed flask equipped with a reflux condenser. The flask was heated in a sand bath until "A" refluxed. It was allowed to reflux at 2540 for three and one-half hours. The cooled material was dis- solved in petroleum ether and washed with two 8 m1. portions of 20% sodium hydroxide, dried over sodium sulfate, and part of the solvent removed. Ninety-one per cent (5.75 g.) of "A", m.p. 470-480, was recovered. The alkaline extracts were acidified and treated with an aqueous bromine solution. Only a trace of phenolic material was present as indicated by the slight loss of color of bromine. Reaction of PhenolL ”A" and Hydrogen Chloride at 1500 Seven grams (0.075 mole) of phenol and 6.6 g. (0.057 mole) of I'A" were placed in the apparatus described by Bordeaux (19). Hydro- gen chloride gas was bubbled through the solution for five and one- half hours at 150°. The mixture remained clear. The cooled mixture was dissolved in 50 m1. of benzene, extracted with two 20 m1. por- tions and one 10 ml. portion of 20% sodium hydroxide, dried over magnesium sulfate, and the solvent removed. The residue was distilled o o $2.!gggg. Four and one-half grams (70%) of "A", b.p. 75 -80 at 1 mm., was recovered. One gram of "A" remained as residue from hold- up in the distillation apparatus. 22. The alkaline extracts were acidified and extracted with four 15 m1. portions of benzene. The combined benzene extracts were dried over magnesium sulfate, the solvent removed and the residue distilled 12.13322. Six and two-tenths grams (88%) of phenol, b.p. 580-62o at 1 mm., was recovered. Attempted Nitration of “A" Method 1. A solution of 5 ml. acetic acid and 1 m1. of nitric acid (d. 1.42) was added slowly to 1.4 g. of "A" dissolved in 5 ml. of acetic acid. The temperature was 150-200. The mixture was allowed to react at room temperature for forty-five minutes and then poured into ice. The solid which separated was recrystallized from petroleum ether. Ninety-six per cent (1.55 g.) of "A", m.p. 460-470. was recovered. The nitration was repeated at higher concentrations of nitric acid and higher temperatures. Again the starting material was recovered in a seventy-one per cent yield. Method 2. One gram of "A" was dissolved in 4 m1. of concen- A light red colored solution was obtained. trated sulfuric acid. Upon the addition of one drop of nitric acid (d. 1.42) the solution became black. The mixture was poured onto ice. The solid which separated was filtered, dissolved in petroleum ether and dried over potassium carbonate. Part of the petroleum ether was removed and the dissolved . (o, nu solid allowed to crystallize. Sixty-five per cent (0.35 O.) of A , m-P- 470-480, was recovered. 25. Reaction of “A1, Hydrobromic Acid, and Acetic Acid Method 1, A solution of 5 m1. of 48% hydrobromic acid, 10 m1. of glacial acetic acid, and 1.2 g. (0.0067 mole) of "A“ was refluxed for twenty-four hours. The solution was cooled, treated with 10% sodium bicarbonate and extracted with two 20 m1. portions of ethyl ether. The combined ether extracts were washed with two 10 m1. portions of sodium hydroxide. The alkaline extracts were acidified and treated with aqueous brominating solution. Eight-tenths gram (55%) of tribromophenol was obtained. Method 2. The experiment was repeated. Four grams of "A", 55 m1. of acetic acid, and 18 ml. of 48% hydrobromic acid were refluxed for thirty hours. The solution was cooled, treated with 10% sodium bicarbonate and extracted with ethyl ether. The other extracts were dried over magnesium sulfate, the solvent removed, and the residue distilled lg 13339. One and two-tenths grams of material, b.p. 1140-128O at 1.5 mm., was obtained. A residue of 2.14 g. remained. The distillate soli- dified, and after several rccrystallizations from petroleum ether melted at 84.50-85.50. This solid will be referred to as "C". The infrared spectrum of "0" had a strong band at 2.73‘p indicating the material was phenolic even though it was isolated from the alkali insoluble fraction. ‘éggl. Calcd. for "C", 012H160: C, 81.77; H, 9.15. Found: C, 81.45; H, 9.40. The alkaline extracts were acidified, extracted with ethyl ether and dried over magnesium sulfate. The solvent was removed and the 24. residue treated with aqueous brominating solution. Less than 0.1 g. of tribromophenol was obtained. The experiment was repeated using 7.7 g. of "A" and the milder conditions found in Method 1. Product "C", m.p. 8AO-859, was obtained from the neutral fraction and l g. of phenol from the alkali soluble fractions. Attempted Reduction of "A“ Ten grams (0.057 mole) of "A" was dissolved in 150 m1. of absolute ethyl alcohol. ?1atinum oxide (0.1 g.) catalyst was added and the mixture was shaken while under a hydrOgen pressure of 5 atmospheres. No hydrogen was absorbed after one-half hour. An addi- tional 0.1 g. of platinum oxide was added, and the mixture again was shaken while under a hydrOgen pressure of 5 atmospheres. No hydrOgen was absorbed. The mixture was transferred to a high pressure bomb and sub- jected to a hydrogen pressure of 500 p.s.i. The mixture was shaken for four hours with no hydrOgen absorbed. The mixture was filtered, the solvent removed, and the starting material, b.p. 81°~8h° at 1 mm., was recovered. erhenoxyé2-methyl-29pentene H -O-0320H20H - C(CH )2 5 A mixture of 95.7 g. (0.7 mole) of potassium carbonate, 47 g. (0.5 mole) of l-chloro-4-methyl-5—pentene, and 140 m1. of acetone were placed in a two-necked flask equipped with a Friedrichs con- denser and a mercury-sealed, motor driven stirrer. The mixture 25. was refluxed on a steam bath for four days. Two gram portions of potassium carbonate were added periodically. The cooled mixture was poured into 200 m1. of water and the organic layer separated. The aqueous layer was extracted with three 100 m1. portions of ethyl ether. The combined organic extracts were washed with 20% sodium hydroxide, dried over sodium.su1fate, and the solvent removed through a glass packed column. The residue was dis- tilled in gggug. l Twenty-eight and six-tenths grams (h8z) of l-chloro~h—methy1- 5-pentene, b.p. 450-50o at 20 mm., was recovered. Thirty-three and five-tenths grams (79% based on used l-chloro-h-methy1-5-pentene) of material, which was shown to be 5-phenoxy-2—methy1-2-pentene, b.p. 85°- 90° at 1 mm., n30 1.5112, was obtained. The experiment was repeated using the same quantities of reagents except that 20 m1. of acetone was added every twenty-four hours during the reflux- ing period. Thirty and nine-tenths grams (52.2%) of 1-chloro~4— methyl-5—pentene was recovered and 20 g. (h7.6% based on used 1- chloro—h-methy1-5-pentene) of 5-phenoxy-2-methyl-Z-pentene was obtained. Anal. Calcd. for 012H150: C, 81.77; H, 9.15. Found: C, 81.76; H, 9.09. Proof of Structure of 5-Phenoxy-2-methyl-Z-pentene fiydrOgenation g; 53phenoxye2-methyl-2-pentene. A mixture of 15.2 g. (0.087 mole) of 5~phenoxy-2-methy1-2-pentene, 170 m1. of absolute ethanol, and 0.2 g. of p1atinum.oxide were placed in a 500 m1. low—pressure reduction bomb. Approximately 0.1 mole of 26. hydrOgen reacted within a period of fifteen minutes. The initial hydrOgen pressure was 12 p.s.i. The catalyst was removed by filtration and the ethyl alcohol was removed through a short Vigreux column. Twelve and two-tenths grams (80%) of a material which was shown to be isohexyl phenyl ether, b.p. 770-80o at 1 mm., n:4.9 1.4885, was obtained. Anal. Calcd. for 012H180: C, 80.85; H, 10.17. Found: C, 79098; H, 10.25. Although the carbon analysis of isohexyl phenyl ether was low, the subsequent series of experiments confirmed the compound as isohexyl phenyl ether. Cleavage g: isohexyl phenyl ether. Twelve and one-tenth grams (0.067 mole) of isohexyl phenyl ether obtained by the reduction of 1-phenoxy-4—methy1-5-pentene, 100 m1. of glacial acetic acid, and 25 m1. of 48% hydrobromic acid were refluxed for nine hours. The mixture was cooled and extracted with six 40 m1. portions of ether. The combined ether extracts were washed with saturated sodium bicarbonate, extracted with 10% sodium hydroxide and dried over magnesium sulfate. The solvent was removed and the residue distilled in vacuo. Seven and one-half grams (58%) of isohexyl bromide, b.p. 55°—60° at 0.1 mm.» “$4.9 mum and 1.5 g- (10%) °f ”6°”er “3°“ hexyl phenyl ether were obtained. The sodium hydroxide extracts were acidified and extracted with ether. The ether extracts were dried over magnesium sulfate, the solvent removed and the residue distilled in vacuo. Three and 2?. eight-tenths grams (50%) of phenol, b.p. 850 at 20 mm., was obtained. Bromination gave 2,h,5-tribrom0phenol, m.p. 92°-95.5°. 5-Methylhexanamide. Six and one-half grams (0.059 mole) of isohexyl bromide obtained from the cleavage of isohexyl phenyl ether, in 25 ml. of anhydrous ethyl ether was added slowly to 1.5 g. (0.05h mole) of magnesium turnings in a round-bottomed three neck flask equipped with a Friedrichs condenser, mercury-sealed, motor-driven stirrer, and an addition funnel. The mixture was refluxed and stirred for two hours. The mixture was cooled to --80 and while being stirred a stream of carbon dioxide gas was passed over the solution until no more white precipitate formed. The mixture was hydrolyzed by slowly adding 100 m1. of 10% sul- furic acid. The ether layer was separated and the aqueous phase extracted with three 50 m1. portions of ether. The combined organic layers were extracted with three 25 m1. portions of 10% sodium hydroxide. The alkaline extracts were acidified and extracted with ether. The ether extracts were dried over magnesium sulfate and the solvent removed. The residue (5 g.) was refluxed with 5 m1. of thionyl chloride for forty-five minutes and then poured into 55 ml. of cold concentrated ammonium hydroxide. The solid which formed was removed by suction filtration, recrystallized from a mixture of ethyl alcohol and water, and dried. The melting point was 101°- 0 102 . The melting point of 5-methy1hexanamide as reported by Levene and Allen (20) is 1020-1050- ...—————;'-——'_' 28. ggaction of_5ePhenoxy-2-methyl-2-pentene, Phenol, and hydrogen Chlo— ride at 150° A mixture of 57.6 g. (0.4 mole) of phenol and 17.4 g. (0.1 mole) of 5-phenoxy-2dmethyl-2-pentene was heated at 1500 while hydrogen chloride was slowly bubbled through the mixture during a seven hour period. The mixture was cooled and dissolved in 100 ml. of benzene. The benzene solution was extracted with three 20 ml. portions of 20% sodium hydroxide, three 20 ml. portions of Claisen's alkali, and dried over potassium carbonate. The solvent.was removed and the residue distilled in 15339. Two and seven-tenths grams of material, b.p. 850-89o at 1 mm., was obtained, which solidified. The material, after recrystallizing from petroleum ether, melted at 470 to 48°. The infrared spectrum was identical with that of the neutral product "A". The alkaline extracts were acidified and extracted with three 50 ml. portions of benzene. The combined benzene extracts were dried over sodium sulfate, the solvent removed and the residue was distilled in xggug. The following fractions were obtained: fraction 1, b.p. 65°- 700 at 1 mm., 29.7 g.; fraction 2, b.p. 700-1100 at 1 mm., 0.4 g.; fraction 5, b.p. 110°-120° at 1 mm., 2.54 g.; fraction A, b.p. 120°- 12500 at 1 mm., 4.47 g. A black residue of 4.58 g. remained. Frac~ tion 1 was recovered phenol (79%). Fraction 5 solidified and after recrystallization from petroleum ether melted at 112°. The infrared spectrum of fraction 5 was identical with “B". 29. I Reaction of_5:Phenoxy-2-methylg21pentene and Hydrogen Chloride at 1500 Ten grams (0.057 mole) of 5-phenoxy-2-methy1-2-pentene was heated at 150° for five hours as hydrOgen chloride was bubbled through the liquid. The mixture was cooled, dissolved in 40 m1. of benzene, and extracted with two 20 m1. portions of 20% sodium hydroxide and one 15 m1. portion of Claisen's alkali. The benzene extract was dried over potassium carbonate, the solvent was removed, and the residue distilled $3 12232. Nine and sevenvtenths grams (97%) of 5-phenoxy-2~methyl-2-pentene, b.p. 90°- 970 at 2 mm., n35 1.5085, was recovered. The alkaline extracts were acidified and extracted with four 25 m1. portions of benzene. The combined benzene extracts were dried over sodium sulfate and the solvent removed. A small amount of residue remained which did react with aqueous bromine. The resi- due was too small to obtain a derivative. Reaction of 5~Phenqu—2—methyl-ngentene with Sulfuric Acid To 2 ml. of concentrated sulfuric (963) was added with shaking 0.45 g. (0.0025 mole) of 5—phenoxy—2-methyl-Z-pentene. The reaction was exothermic and a red color developed. The mixture stood three minutes and was poured onto 5 g. of ice. A white solid (0.28 g.) separated. It was filtered, dried, and recrystallized from petroleum ether. The melting point was 460-470; mixed melting point of the pro- duct with "A" was 470-480. The infrared absorption spectrum of the Product was identical with that of "A". Two drOps of concentrated sulfuric acid was added to 0.5 m1. of 5-phenoxy-2-methyl-2-pentene. After shaking for approximately one minute, 10 m1. of water was added. "A" separated as white plates in a good yield. Reaction of Isohexyl Phenyl Ether with Sulfuric Acid One-half gram of isohexyl phenyl ether was dissolved in 2 ml. of sulfuric acid. A slight red color developed.‘ The mixture was poured into 10 g. of ice, and an oil separated. The mixture was made alkaline with sodium hydroxide and then extracted with petro- leum ether. The organic extracts were dried over potassium carbon- ate and the solvent removed. The residue (0.4 g.) was a clear liquid, n35 1.4890 which was recovered (80%) isohexyl phenyl ether, n§4.9 1.4885. The alkaline extracts were acidified and indicated no phenolic material present when tested with phosphomolybdate (22). t- Butyl Phenyl Ether The procedure of Stevens and Bowman (21) was followed. Ninety- four grams (1.0 mole) of phenol and 52 mg. of concentrated sulfuric acid were placed in a 500 ml. round—bottomed flask equipped with a gas inlet tube, a ground glass stirrer, and a dry ice condenser. The phenol was melted and a stream of isobutylene was passed through the stirred solution as it was quickly cooled to 50 to 8°. The isobutylene was passed into the slurry only as rapidly as it was absorbed. Fifty-eight grams (1.04 moles) of isobutylene was absorbed in five hours. Three hundred milliliters of 10% sodium hydroxide was added and the organic layer was dissolved in 150 m1. of ether. The organic 51. layer was separated, extracted with four 50 ml. portions of Claisen's alkali, and dried over sodium sulfate. The solvent was removed and the residue distilled ig_vacuo. Forty—six and four-tenths grams (56.9% based on used phenol) of tfbutyl phenyl ether, b.p. 720_7§o at 17 mm., 11%14 1.4855, was obtained. This product gave a negative test with phosphomolybdate test, Platkovskaya and Vatkina (22). The infrared spectrum also showed no phenolic material being present. Forty-three grams (45.7%) of phenol, b.p. 850-90o at 20 mm., was recovered. The experiment was repeated except that the product was washed with 10% sodium hydroxide only. The product obtained contained con- siderable amounts of phenol, and after extracting with Claisen's alkali 20 g. (15.5%) of t-butyl phenyl ether, b.p. 750-750 at 16 mm., n35 1.4850, was obtained. Stevens and Bowman reported a yield of 69.2% based on phenol consumed. Reaction of t-Butyl Phenyl Ether and HydrOgen Chloride at 50° Ten grams (0.067 mole) of tvbutyl phenyl ether in 10 m1. of benzene was heated at 500 for forty-five minutes while hydrOgen chloride gas was bubbled through the solution. The mixture was cooled, extracted with 20% sodium hydroxide, and dried over anhydrous potassium carbonate. The solvent was removed and the residue dis- tilled lg vacuo. Three and three-tenths grams (55%) of t—butyl phenyl ether, b.p. 720-750 at 15 mm., n35'1.485l, was recovered. The alkaline extracts were acidified and extracted with four 20 m1. portions of benzene. The combined benzene extracts were dried over sodium sulfate, the solvent removed, and the residue recrystallized 52° from petroleum ether. Two and two-tenths grams (24%) of phenol, m.p. 59°-uo°, was obtained. The tribromo derivative melted at 95°~94°. o-fiydrqustynyl IsOprgpyl Ketone OH ( \\\ CH=CHCOCH(CH5)2 The general experimental conditions of Harries and Busse (25) were used. Fifty grams (0.41 mole) of salicylaldehyde was dissolved in a solution of 50 m1. of ethyl alcohol and 140 ml. of 10% sodium hydroxide. Fifty grams (0.58 mole) of methyl isoprOpyl ketone and 250 ml. of 10% sodium hydroxide was added. The solution was diluted with water to 2 l. and allowed to stand in the dark for eight days. The solution was acidified with dilute hydrochloric acid and the precipitate was removed by filtration. The solid was dissolved in hot benzene and the solution decolorized with Norite. Upon cool- ing the benzene solution, 55 go (45%) of‘gfhydroxystyryl isOprOpyl ketone, m.p. 104.50-105.5o was obtained. McGookin and Sinclair (24) report for g—hydroxystyryl isOpropyl ketone, m.p. 107°. The experiment was repeated four times using the same amounts of starting materials. The yields of g—hydroxystyryl isopropyl ketone varied from 58.4% to 51.5%. 13(ojfiydroxyphenyl)34-methy1-5fipentanone 0s ,/’ CH CH cocs(cw3)2 2 2 ‘\\ 55- Nineteen grams (0.1 mole) of gehydroxystyryl iSOprOpyl ketone was dissolved in 70 m1. of absolute ethanol. Two tenths gram of platinum oxide was added and the mixture reduced with hydrOgen under a pressure of approximately two atmospheres. One-tenth mole of hydrOgen was absorbed within forty minutes. The catalyst was removed by filtration, the solvent was dis- tilled, and the residue distilled ig 13323. Fifteen grams (70%) of l-(grhydroxyphenyl)-4~methyl-5—pentanone, b.p. 1210-125o at 1 mm., was obtained. The l-(g—hydroxyphenyl)-4—methyl-5-pentanone crystal- lized slowly, and after several recrystallizations from petroleum ether melted at 450-470; 2,4-dinitr0phenylhydrazone, m.p. 1460-1470. Igggl. Calcd. for 012H160’ C, 74.95: H, 8.59. Found: C, 75.59; H, 9.5. Calcd. for 08H20N405: C, 58.06; H, 5.41; N, 15.04. Found: c, 58.54; H, 5.86; N, 14.78. Since the analyses were not too satisfactory, the methyl ether was prepared and the dinitrophenylhydrazone derivative made. The melting point of the dinitrOphenylhydrazone was ll5.5°—116.5°; mixed melting point with a known sample was 115.50-116.5°, (see page 41, Method 1.) The experiment was repeated two times using 17 g. and 50 g. of grhydroxystyryl isOprOpyl ketone. Seventy per cent yields of 1-(9— hydroxyphenyl)-4~methyl—5-pentanone were obtained in each experiment. 2-Isgpropylchroman o\~CH(CE-I)2 51+. Eighteen grams (0.094 mole) of 1-(2-hydroxyphenyl)-4-methy1-5- pentanone was dissolved in 250 ml. of ethyl alcohol in a l 1. round- bottomed flask equipped with a motor-driven stirrer, a reflux con- denser, and an addition funnel. Sixty grams (0.94 mole) of zinc dust was added and then 80 m1. of concentrated hydrochloric acid was added slowly with stirring. An additional 20 g. (0.51 mole) of zinc dust and 50 m1. of concentrated hydrochloric acid was added. The mixture was refluxed for twenty-four hours. The mixture was cooled, filtered, and water was added. The solution was extracted with six 50 m1. portions of benzene. The combined benzene extracts were washed with 20% sodium hydroxide, dried over potassium carbonate, and the solvent removed. The residue was distilled 33.35332, and 7 g. (42.4%) of 2~ isOprOpylchroman, b.p. 950-1050 at 1 mm., was obtained. The product was redistilled and 5.5 g. of 2-is0propylchroman, b.p. 950-98o at 1 mm., n35 1.5155 was obtained. I 529;. Calcd. for 0121-1160: c, 81.76; H, 9.15. Found: c, 81.58; H, 9.16. Experiments Concerning Phenolic Product "8" Derivatives of ”B" Phenoxyacetic acid derivative 2£.:§:' The procedure of Koelsch (25) was followed. One gram of "B" was dissolved in 5.5 m1. of 55% sodium hydroxide. Four milliliters of water was added to completely dissolve "8". Two and one-half milliliters of 50% chloroacetic acid in water was added and the mixture heated for two hours on a steam 55- bath. The mixture was cooled and acidified with dilute nitric acid to the congo-red end point and extracted with ether. The ether extracts were washed with water and then extracted with 20% sodium carbonate. The sodium carbonate extracts were acidified and the solid removed by filtration. The crude acid was recrystallized from water and dried. The melting point of the phenoxyacetic acid (0.9 g.) was 141° to 142°. A weighed sample (0.2814 g.) of the phenoxyacetic acid was dis- solved in 100 ml. of 50% ethyl alcohol and water. One-half aliquot portions were titrated with 0.0555 N sodium hydroxide, using a Beck- mann pH meter. The neutralization equivalents found were 255.2 and 256.7. The neutralization equivalent calculated for C6HllC6HAOCH200 H 2 is 254.1. Angaphthyl urethan g: "B". The procedure of Shriner and Fuson (25) was followed. One-half gram of "B", 0.5 g. off -naphthyl iso- cyanate and 2 drops of pyridine were dissolved in 10 ml. of benzene. The mixture was refluxed overnight. The benzene was removed and the residue treated with petroleum ether. The white solid was recrystal- lized from ethyl alcohol five times. The melting point of the I5~naphthyl urethan of "B" remained constant at 1640-155o after the fourth recrystallization. ‘éggl. Calcd. for C25H2§N028 C, 79.95; H, 5.71. Found: C, 79.48; H, 6.99. Benzoate g; 1&1. One gram of benzoyl chloride was heated cau- tiously with 1 g. of "B". The mixture was poured into water. The oil which formed was treated with 5% sodium carbonate. The solid 56. which slowly separated was recrystallized from water and ethyl alcohol four times. The melting point of the benzoate of "B” was 84° to 85°. ‘5231. Calcd. for 019H2002: C, 81.40; H, 7.19. Found: C, 81.15; H, 7.27. Oxidation of “B" with Permanganate The general procedure of Eleuterio (27) was followed. To a solution of {.7 g. (0.05 mole) of "E" in 250 m1. of acetone was added drOpwise and with stirring a solution of 71.1 g. (0.45 mole) of potassium permanganate in 1.2 l. of water. The temperature was kept at 100 to 15°. The mixture was stirred forty-five minutes and then acidified with 5 N sulfuric acid. Sodium bisulfite was added to decompose the manganese dioxide. The mixture was extracted With five 100 ml. portions of benzene. The combined benzene solu- tions were extracted with five 50 m1. portions of 10$ sodium bicarb- onate. The combined sodium bicarbonate extracts were seidified With 5 N sulfuric acid and extracted with five 40 ml. portions of benzene. The combined benzene extracts were dried over sodium sulfate and the solvent removed through a Vigreux column. he residue could not be distilled without decomposition. The . t ' 0 - . . - »+' ‘ One milliliter 0. reaction was repeated using tne same quantities. u "‘ ‘ xed an oil remained after removing the benzene. the 011 was refhd with 4 ml. of thionyl chloride for twenty minutes and then poured ' . ' . . 'de A brown solid Into 20 m1. of cold concentrated amhonium hydrox1 . 1200, would not 0 with some oil formed. The crude solid, m-P- 115 to ' 1 A a Th0 recrystallize from a mixture of ethyl alcohol and water 57 . material normally separated as a very fine solid which would not filter readily or separated as an oil. Chloroform and petroleum ether were tried as solvents. The crude solid was too soluble in chloroform and insoluble in petroleum ether. The mixture of chloro— form and petroleum, also, was unsuccessful. Iiitrosation of '13: Method 1. The general procedure of Hodgsen and Nicholson (28) was followed. One and one-tenth grams of "B" was dissolved in a mixture of 12 m1. of water and 20 ml. of acetic acid. A solution of 2.5 g. of sodium nitrite in 10 m1. of water was added slowly at -20 to the solution of "B", acetic acid, and water. The solution became reddish brown immediately. The mixture was allowed to stand for three hours in an ice bath. The red solid which separated was removed by filtration. The solid was recrystallized from acetic to give red crystals, m.p. 1850 with decomposition. .gggl. Calcd. for 012H15NO2: C, 70.22; H, 7.56; N, 5.82. Found: 0, 77.553 H, 7.56; N, 2.10. The unsatisfactory analyses of the product was not entirely unexpected in view of the results obtained in attempted nitrosations on.g:trbutylphenol which are described below. Method 3' The general procedure found in Organic Syntheses (29) was followed. Eight grams of "B" was dissolved in 80 m1. of ethyl alcohol. Forty milliliters of concentrated hydrochloric acid was added to the stirred solution. Four and seven—tenths grams of sodium nitrite was added slowly to the stirred ice cold solution. The mix- rL . 1 ture was then stirred for twenty-four hours. 58. The mixture was poured into 500 ml. of water. A viscous oil separated. The water was decanted and the oil dissolved in acetic acid. Two grams of a black hard crystalline solid separated. After the second recrystallization from acetic acid the color of the crys- tals became dark red brown, m.p. 1140-1500. Attempts at further purification were unsuccessful. Attempted Nitrosation of m-tPButylphenol Method 1. One gram of metrbutylphenol was dissolved in 5 m1. of 95% ethyl alcohol. The solution was stirred and cooled to 00 and 5 m1. of concentrated hydrochloric acid was added. Sodium nitrite (0.72 g.) was added to the cooled solution and the mixture allowed to stand overnight. The mixture was poured into water. An oil separated which solidified after cooling for four days. The solid was removed by filtration and recrystallized from acetic acid. The solid, when dried in a vacuum desicator over calcium oxide, slowly turned to an oil. Method 2. The general procedure of Hodgson and Nicholson (28) was followed. A solution of 2 g. of sodium nitrite in 5 ml. of water was added drOpwise to a solution of 1 g. of Effi’bUtYlthHOI’ 21 ml. of acetic acid, and 12 ml. of water at ~20. The mixture was stirred at room temperature for twenty hours. Approximately 0.5 ml. of a dark oil separated which did not solidify. Methylation of "B" To a stirred solution of 9.55 g- (0.055 m°1°) 0f "3": 5.4 g- (0.085 mole) of sodium hydroxide, and 25 ml. of water was added, slowly, 8.2 g. (0.055 mole) of methyl sulfate. The mixture was heated with stirring on a steam bath for three hours and forty-five minutes. The mixture was cooled, 50 ml. of 10% sodium hydroxide was added, and the whole then extracted with ether. The combined ether extracts were washed with 5 m1. portions of 10% sodium hydroxide until no further phenolic material was removed. The ether extracts were dried over magnesium sulfate, the solvent removed, and the residue distilled in 13322. Four and eightptenths grams (46%) of the methyl ether of "B", b.p. 810-92o at 1 mm., n35 1.5515, was obtained. .Aggl. Calcd. for 0153180: 0, 82.10; H, 9.55. Found: C, 82.01; H, 9.41. The reaction was repeated using 22.5 g. (0.126 mole) of "B". The yield of product was 10.75 g. (h5%). Oxidation of the Methyl Ether of is: Five grams (0.024 mole) of the methyl ether of “B" was dis- solved in a mixture of 55 ml. of acetone and 50 ml. of water. The solution was stirred and cooled to 10°. Twenty and two-tenths grams (0.128 mole) of potassium permanganate was added during a six hour period. The temperature was allowed to increase to 250 during the addition. The mixture was allowed to stand overnight. The mixture was filtered and the manganese dioxide cake was washed with water and then acetone. Part of the acetone was distilled from the filtrate; then the filtrate was acidified and extracted with three portions of benzene. The combined benzene extracts were ho. extracted with 20% sodium hydroxide, dried over sodium sulfate, and the solvent removed. One and three-tenths grams of an oil residue remained. The sodium hydroxide extracts were acidified and extracted with ether. The ether extracts were dried over magnesium sulfate and the solvent removed. Approximately 1 m1. of an oily residue remained. The residue did not crystallize. The reaction was repeated using 4.82 g. (0.025 mole) of "B" and 19.9 g. (0.126 mole) of potassium permanganate. The same type of residues were obtained. The residue from the alkali soluble fraction was a viscous oil which did not crystallize. The residues in each instance were dark colored. 2:Methoxystyry1 leoprOpyl Ketone \ cscncocrfi 0:192 / l A solution of 25.9 g. (0.126 mole) of g—hydroxystyryl isOpropyl ketone, 50 m1. of methyl alcohol, and 16 g. (0.15 mole) of methyl sulfate was stirred and cooled to -5°. A cold solution of 11.25 g. (0.2 mole) of potassium hydroxide in 26 ml. of water was added in one portion. The temperature increased to 54°. The mixture was stirred at room temperature for two and one-half hours. One hundred milliliters of water was added and the mixture extracted with three 50 m1. portions of benzene. The combined 1! 41. benzene extracts were washed with 20% sodium hydroxide, dried over potassium carbonate, the solvent removed, and the residue distilled 19 33339. Eleven and eight-tenths grams (75% based on starting material consumed) of g—methoxystyryl isOpropyl ketone, b.p. 155°- 1610 at 1.8 mm., ngso 1.5758, was obtained. The alkaline extracts were acidified, and 7.5 g. (55.8%) of grhydroxystyryl isOprOpyl ketone was recovered. The semicarbazone of g—mathoxystyryl isopropyl ketone was pre- pared by the procedure of Gheorghiu (50), m.p. 1820 to 185°. Gheorghiu reported the melting point was 1790 to 181°. The experiment was repeated two times using 48 g. (0.25 mole) of g-hydroxystyryl isOprOpyl ketone. The yields varied from 75% to 95% based on the amount of starting material consumed. 1-(o-Methoxypheny1):h-methylg5gpentanone OH I 5 o .~.CH20H2000H(CH5)2 Method 1. The general procedure of Perkin and Weizmann (51) was followed. Sixteen grams (0.082 mole) of 1-(grhydroxyphenyl)-4- methyl-5-pentanonc, 50 m1. of methyl alcohol, and 10.1 g. (0.082 mole) of dimethyl sulfate were stirred and cooled to -5°. Nine and two-tenths grams (0.164 mole) of potassium hydroxide dissolved in 21 ml. of water was added in one portion. The temperature increased 0 to 28 . The mixture was stirred for two hours at room temperature. 42. Fifty milliliters of water was added and the mixture was extracted with three 50'm1. portions of benzene. The combined benzene extracts were washed with 20% sodium hydroxide, then Claisen's alkali, and dried over potassium carbonate. The solvent was removed and the residue distilled in 33233. Seven and four-tenths grams (45.8%) of l-(g-methoxyphenyl)-4~methyl-5—pentanone, b.p. 1200-122o at 2 mm., was obtained. The melting point of its 2,4-dinitr0pheny1hydrazone was 115.50 to 116.50. The mixed melting point with an analyzed sample was 115.50 to 115.50. Method 2. Twenty grams (0.1 mole) of grmethoxystyryl isOprOpyl ketone, 80 m1. of ethyl alcohol, and 0.2970 g. of 5% palladium on carbon were placed in a 500 m1. low-pressure hydrOgenation bomb. One-tenth mole of hydrOgen was absorbed in thirty-five minutes. The catalyst was removed by filtration and the solvent distilled. The residue was distilled 13 13329. Nineteen and one-tenths grams (92.7%) of l-(grmethoxyphenyl)-4-methy1-5—pentanone, b.p. 155o_1450 at 2 mm., was obtained. The reduction was repeated using 41 g. (0.2 mole) of g—methoxystyryl isOprOpyl ketone. Forty grams (97%) of l- (g-methoxyphenyl)-4~methy1-5-pentanone was obtained. The product was redistilled through an 8 inch heated Vigreux column. The pure product had the following physical constants; b.p. 1210-125o at 2 mm., ng5o 1.5082. The dinitrOphenylhydrazone, after several recrystallizations from ethyl alcohol, melted at 115.5° to 115.5°. 45. .5251. Calcd. for 015H1802’ C, 75.70; H, 8.79. Found: 0, 75.56; H, 8.74. Calcd. for 019H22N405: 0, 59.05; H, 5.74; N, 14.50. Found: 0, 58.66; H, 6.68; N, 14.25. The unsatisfactory hydrOgen analysis of the dinitrophenylhydra- zone derivative could not be explained since the parent ketone analyzed correctly. After reduction of the carbonyl group to the alcohol in the following experiment, the analysis of the alcohol and the phenyl urethan derivative were satisfactory. lio-Ivfeth oyph enyl )«4-methy1-5-pgntanol CH 1 5 0 \ ((8 - —.~ CHZCHZCHOHCH(CH§)2 Four grams (0.106 mole) of lithium aluminum hydride was dis- solved in 500 ml. of anhydrous ether in a l l. flask equipped with a Friedrichs condenser, a mercury-sealed motor stirrer, and an addi- tion funnel. Forty—nine grams (0.25 mole ) of 1-(2rmethoxyphenyl)- 4—methy1—5-pentanone in 500 ml. of anhydrous ether was added during a period of one hour. The mixture was allowed to stand overnight. The mixture was hydrolyzed by the cautious addition of 50 ml. of water and then 200 m1. of 10% sulfuric acid. The organic layer was separated, and the aqueous layer extracted with two 100 m1. portions of ether. The combined organic extracts were dried over sodium sulfate, the solvent removed, and the residue distilled in vacuo through an 8 inch heated Vigreux column. Eighty-two and 44. one-half per cent (42.85 g.) of l—(g-methoxyphenyl)-4-methy1—5- pentanol, b.p. 1190-125o at 1 mm., ngfi's 1.5151, was obtained. The phenyl urethan was made by the general procedure of Shriner and Fuson (26), m.p. 750 to 76°. ‘éngl. Calcd. for 015H2002: C, 74.96; H, 9.68. Found: C, 74.97: H, 9.85. Calcd. for 0201125305: 0, 75.56; H, 7.70; N, 4.28. Found: C, 75.56; H, 7.66; N, 4.52. Dehydration of 1-(o4Methoxypheny1)-4-methylz5gpentanol A mixture of 1 g. of concentrated sulfuric acid and 21.55 g. (0.108 mole) of 1-(2-methoxypheny1)~4-methyl-5-pentanol was placed in a 50 ml. round-bottomed flask. The mixture was distilled slowly through an eight inch heated Vigreux column. Fourteen and eight— tenths grams (7237.) of material, b.p. 95°-105° at 1 mm., was obtained. The experiment was repeated twice using a total of 17.7 g. of alcohol and 15.58 g. (84%) of material, b.p. 950-1050 at 1 mm., was obtained. The products were combined, dissolved in ethyl ether, extracted with sodium bicarbonate, dried over anhydrous potassium carbonate, and the solvent removed. The residue was distilled 12.22222 in a semi-micro distillation apparatus. The following fractions of 4 ml. each were obtained: fraction 1, b.p. 880-90o at 1 mm., n35 1.5252; fraction -2, b.p. 900-940 at 1 mm., n35 1.5248; fraction 5, b.p. 920 at 0.9 mm., n35 1.5270; fraction 4, b.p. 920-95? at 1 mm., n35 1.5290; fraction 5, b.p. 950-98o at 1 mm., n35 1.5520. The constant increase of the refractive index indicated the unsaturated material was a mixture of isomers. The bromine number of fractions 2 and 4 was obtained 45. by the procedure of Johnson and Clark (52). The calculated bromine number for 5-(2-methoxyphenyl)-2-methy1-2-pentene or an isomer is 84.1 Found for fraction 2: 78.6; 79.4. Found for fraction 4: 85.9; 85.4. penethoxystyryl Isopropyl Ketone cs5o Q cszcncocswsjb Forty-seven grams (0.55 mole) of anisaldehyde and 25 g. (0.55 mole) of methyl isOprOpyl ketone, and 250 ml. of ethyl alcohol were placed in a 500 m1. flask. Fifteen milliliters of 10% sodium hydrox- ide was added with shaking and the mixture was allowed to stand for one day. Two hundred milliliters of water was added and the oil extracted with benzene. The benzene extracts were dried over potassium carbon- ate, the solvent removed and the residue distilled igngggg through a Claisen head. Thirty-seven and four-tenths grams (60%) of p- methoxystyryl isOprOpyl ketone, b.p. 1200-160o at 2 mm., was obtained. The experiment was repeated using 42 g. (0.507 mole) of anisalde- hyde and 57 g. (59%) of the product was obtained. One run using 68 g. (0.5 mole) of anisaldehyde gave only 17.7 g. (17.4%) of the product when the reaction time was decreased to three hours. The combined product from the three eXperiments (92 g.) was redistilled through and eight inch heated Vigreux column. Sixty—nine grams of product, b.p. 1550-160o at 2 mm., m.p. 28° to 500 was obtained. Vorlander and Knotzsch (55) reported for pomethoxystyryl isOprOpyl o o ketone, b.p. 2170-219 at 40 mm., m.p. 28 . 1-(p-Methoxyphenyl)—4~methy1:5rpentanone csio CH20H2000H(CH5)2 Sixty-nine grams (0.555 mole) of pfmethoxystyryl i80pr0py1 ketone, 200 m1. of ethyl alcohol, and 0.50 g. of platinum oxide were placed in a 500 m1. low pressure hydr0genati0n bomb. The mix- ture was shaken at an initial hydrOgen pressure of 49.5 p.s.i. The reduction was stOpped when approximately 0.54 mole of hydrOgen had been absorbed (one hour). The catalyst was removed by filtration, the solvent removed, and the residue distilled in 15922 through an eight inch Vigreux column. Sixty-five grams (95% of l-(pf methoxyphenyl)-4-methyl-5-pentan0ne, b.p. 1280-129o at 1 mm., r1393)+ 1.5082, was obtained. .égal. Calcd. for 015H1802: C, 75.69; H, 8.79. Found: C, 76.17, 76.41; H, 9.50, 9.25. The discrepancies in the analyses cannot be explained by incomplete reduction occurring or by reduction of the carbonyl as well as reduction of the carbon double bond. The alcohol obtained by reducing the above ketone with lithium aluminum hydride had a satisfactory analysis (see page 47)- 47. 1-(prMethoxypheny1)-4-methy1e51p§ntano1 onio. CH20H2CH0HCH(CH5)2 Sixty-three grams (0.506 mole) of 1-(pfmethoxypheny£}4-methyl— 5-pentanone in 150 ml. of anhydrous ether was added slowly to a stirred solution of 5.7 g. (0.15 mole) of lithium aluminum hydride in 250 ml. of anhydrous ether. The mixture was stirred at room temperature for four hours and then heated for one hour. The excess lithium aluminum hydride was destroyed by the addi- tion of 5 ml. of ethyl acetate and then 50 m1. of water. The mix- ture was hydrolyzed with 200 m1. of 10% sulfuric acid. The organic layer was separated, and the aqueous layer extracted with two 100 m1. portions of ether. The combined organic extracts were dried over potassium carbon- ate, the solvent removed, and the residue distilled through an eight inch heated Vigreux column in 35332. Fifty and four-tenths grams (50.8%) of l-(pfmethoxyphenyl)-4-methyl-5-pentanol, b.p. 125°-127° at 0.6 mm., ngj'a 1.5151, was obtained. The phenyl urethan, m.p. 66.50 to 67.50, was prepared by the general procedure of Shriner and Fuson (26). Anal. Calcd. for Cl5fi2002‘ C, 74.96; H, 9.68. Found: C, 74.68; H, 9.60. Calcd. for Czoszslzoi: c, 75.56; H, 7.70; N, 4.28. Found: C, 75.65; H, 7.46; N, 4.18. Dehydration of 1-(p-Methoxypheny1)y4-methy175jpentanol The general experimental condition of Whitmore and Simpson (54) 48. were used. Fifty grams (0.24 mole) of the alcohol was dissolved in 140 m1. of anhydrous other were placed in a 500 m1. round-bottomed flask equipped with a reflux condenser, a motor stirrer, and an addition funnel. The condenser was fitted with a.calcium chloride drying tube. A slurry of 10 g. (0.25 mole) of powdered sodium hydrox— ide and 12 ml. of carbon tetrachloride was added, and the mixture was stirred for forty minutes. Eighteen and two—tenths grams (0.24 mole) of carbon bisulfide was added over a period of twenty minutes, and the mixture was stirred an additional five hours. A pink precipitate formed. Thirty-four grams (0.24 mole) of methyl iodide was added slowly and the mixture was stirred overnight and then refluxed for eight hours. The inorganic salts were removed by filtration and the solvent removed. The methyl xanthate decomposed when distillation was attempted at 1 mm. The residue was then heated at 1700-180o at 20 mm. until the vigorous evolution of gases ceased (one hour). The residue was then distilled, b.p. 1750-1800 at 18 mm. The distillate was dissolved in 50 m1. of benzene, washed with two 50 ml. portions of 40% potassium hydroxide, one 50 ml. portion of water, and with a saturated mercuric chloride solution. It was then washed with 20 m1. of water, dried over sodium sulfate, filtered, and redried over sodium sulfate. The solvent was removed and the residue distilled through a heated Vigreux column 22.12222“ The following fractions were obtained: fraction 1, b.p. 1050-105o at 2 mm., ngh'5 1.5160, 1 g.; fraction 2, b.p. 1050-106O at 2 mm., n24.5 24.5 0 0 D 1.5086, 5.04 g.; fraction 5, b.p. 105 —106 at 2 mm., nD 49. 1.5090, 2.24 g.; fraction 4, b.p. 1060-1590 at 2 mm., ngh'fi 1.5442, 5.8 g.; fraction 5, b.p. 1590-140o at 2 mm., ngh°5 1.5148, 22 g. Fractions 4 and 5 (51.5%) were essentially pure recovered alcohol, n33'8 1.5151. Fractions 2 and 5 (28.5% based on alcohol used) were later shown to be the unsaturated material. The reaction was repeated using 25 g. (0.12 mole) of the 1-(pf methoxyphenyl)~4-methy1—2-pentanol. After the addition of carbon bisulfide the mixture was stirred overnight instead of only five hours. The reaction was treated as previously described. Seven and one-half grams of material, b.p. 1000-110o at 2 mm., was obtained. This material was redistilled and 5 g. (21.9% based on alcohol used) of unsaturated material, b.p. 900-1000 at 0.7 mm., n§u°6 1.5090 was obtained. Ten gram (40%) of crude alcohol was recovered. In the distillations small foreruns were obtained which were consistently yellow and decomposed to give a yellow inorganic precipitate. The products were combined and redistilled through the semi- micro distillation apparatus lfl.l§£22° The following fractions were obtained: fraction 1, b.p. 850-90o at 0.9 mm., ngso 1.5098, 1.28 g.; fraction 2, b.p. 90°—95° at 1 mm., n35 1.5092, 1.05 g.; fraction 5, b.p. 950 at 1 mm., n35 1.5096, 2 g.; fraction 4, b.p. 95°~97° at 1 mm., 11?? 1.5097, 0.75 g. All fractions had a small amount of suspended solid in them. Since the refractive index was not constant a mixture of the unsaturated compounds, 5~(pfmethoxypheny1)—2-methyl-2~pentene and 1-(Efmethoxyphenyl)-4‘methy1-5-pentene, was apparently obtained. 50. The bromine number was obtained by the procedure of Johnson and Clark (52). The calculated bromine number for 0153180 is 84.1. Bromine number found: 85.7, 85.5. Ethyl 2—Carbethoxyj5émethyle5ephenylbutanoate Q _ C( CH5)2CH( 00202115 )2 One hundred and fifty-six and nine-tenths grams (1 mole) of bromobenzene in 500 m1. of anhydrous ether was added dropwise to 25.5 g. (1.04 moles) of magnesium turnings in a 2 1. round-bottomed flask equipped with a Friedrichs condenser, mercury-sealed motor stirrer, and addition funnel. The mixture was stirred for one hour at room temperature and then one hour with refluxing on a steam bath. The mixture was cooled in an ice bath and 190 g. (0.95 mole) of ethyl isOpropylidene malonate [prepared from acetone, malonic ester and zinc chloride (55) 1 in 200 m1. of anhydrous ether was added over a two hour period. The mixture was stirred at room temperature for two and one-half hours. The mixture was hydrolyzed by the addition of 400 ml. of 10% sulfuric acid. The organic layer was separated and the aqueous layer extracted with three 100 m1. portions of ether. The combined organic extracts were dried over sodium sulfate, the solvent remOVpd, and the residue distilled through a Claisen head 33 33532. Ninety and two-tenths grams (50%) of the ethyl 2-carbethoxy—5- methyl-5—pheny1butanoate, b.p. 145°—l50° at 0.5 mm., ng5'5 1.4982, was obtained. A forerun of 74.1 g., b.p. 1020-145o at 0.5 mm., was 51. obtained also. Prout, gt El° (56), report for the product, b.p. 1770-178o at 18 mm., n35 1.4959, and obtained an average yield of 40% based on two runs. The experiment was repeated using the same quantities and 55 g. (21%) of the product obtained. 2-Hydroxymethy1157methyl-5gphenyl-l-butanol C(CH5)20H(CH2OH)2 The general procedure of Pines, gt El. (57) was used. Ninety grams (0.52 mole) of ethyl 2-carbethoxy-5-methy1-5-pheny1butanoate in 150 m1. of anhydrous ether was added slowly to a stirred solu- tion of 18.95 g. (0.5 mole) of lithium aluminum hydride in 650 m1. of other. The mixture was stirred seven hours. Ethyl acetate was added to decompose the excess lithium aluminum hydride. The mixture was hydrolyzed by the addition of 400 m1. of 10% sulfuric acid. 'The organic layer was separated and the aqueous phase extracted with two 100 ml. portions of ether. The combined organic extracts were dried over magnesium sulfate, the solvent removed, and the residue distilled in 12333 through a Claisen head. Fifty~one grams (82%) of 2-hydroxymethyl-5-methyl-5-pheny1-l-butano1, b.p. 1650-17140 at 0.9 mm., was obtained. The product, which slowly crystallized, was recrystallized twice from petroleum ether, m.p. 62.50 to 64°. The experiment was repeated using 52 g. (0.18 mole) of the malonic ester and 11.27 g. (0.5 mole) of lithium aluminum hydride. Twenty-eight grams (81%) of the diol was obtained. 52. Anal. Calcd. for 012H18O2: C, 74.19; H, 9.54. Found: C, 74.45; H, 9.25. 2-Bromomethylg5rmethy1:5:pheny1-1-bromobutane C(CH5)20H(CH28r)2 The general procedure of Pines, 33.3l. (57) was followed. Eighteen and four-tenths gram (0.1 mole) of 2-hydroxymethyl-5- methyl-5-phenyl—l-butanol was heated to 700 in a 500 m1. round- bottomed flask equipped with a Friedrichs condenser, a motor stirrer, and an addition funnel. With vigorous stirring 19.76 g. (0.075 mole) Of phosphorus tribromide was added at such a rate that the tempera- ture of the mixture remained at 70°. The mixture was then stirred at 70° for one hour and then heated on the steam bath overnight. The cooled mixture was poured into a slurry of ice and water. The mixture was extracted with two 60 m1. portions of benzene. The e . 1, combined benzene extracts were washed successively with water, 10p potassium carbonate, and then water until the aqueous washings were neutral to litmus. The benzene extracts were dried over calcium chloride, the solvent removed, and the residue distilled i3 vacuo. o Nineteen and six-tenths grams (65%) of the product, b-P- 150 ' 26 1600 at 1 mm., nD 1.5672, was obtained. One gram of a viscous residue remained. The experiment was repeated using 52 g. (0.174 3016) Of the diol and 54.7 g. (0.128 mole) of phosphorus tribromide. The yield 0 o u. - "33 24.7 g. (46%) of dibromide, b.p. 160 —l62 at 1.6 mr Five 55. grams of a viscous residue remained. The product was analyzed for bromine by the method of Umhoefer (58). Anal. Calcd. for 012H183r2’ Br, 49.65. Found: Br, 49.2; 48.7. Dimethylcyclapropylcarbinylbenzene —* CH /’ The general experimental conditions of Shortridge, gt 2l° (59) were used. Thirty—two grams (0.48 mole) of zinc dust and 500 m1. of 80% ethyl alcohol were placed in a 500 ml. round-bottomed flask equipped with a Friedrichs condenser, a mercury-sealed motor stirrer, and an addition funnel. The mixture was brought to reflux and with vigorous stirring 52 g. (0.1 mole) of 2-bromomethyl-5-methyl-5- phenyl-l-bromobutane was added over a period of one and one-quarter hours. The heating and stirring was continued for twenty-four hours. The mixture was cooled and filtered. The excess zinc and zinc bromide was washed with benzene. The benzene washes and filtrate were combined, and the organic layer separated. The aqueous layer was then extracted with benzene. The combined organic extracts were dried over calcium chloride, the solvent removed through a Vigreux column, and the residue distilled in vacuo through a semi- micro distillation apparatus. Eleven and three-tenths grams (71%) of dimethylcycl0pr0pylcarbinylbenzene, b.p. 950-98o at 12 mm., 2 . nDh 8 1.5155, was obtained. One and one-half grams of material, 54. b.p. 980-1500 at 12 mm., was obtained and a residue of 1.4 g. remained which did not distill. The experiment was repeated using 45.7 g. (0.157 mole) of the dibromide. Nineteen and two-tenths grams (87%) of the product, b.p. 92°-98° at 12 mm., was obtained. This material was redistilled through a small Vigreux column yielding 15.5 ml. of product, b.p. 94° at 12 mm., 1112;” 1.5150. A forerun of 1.4 m1., b.p. 92°-94° at 12 mm., n34-5 1.5105, was obtained. A residue of 1.5 g. remained which was distilled in the semi-micro distillation apparatus; approxi- mately 0.5 g. of material, b.p. 940-98o at 12 mm., n34-5 1.5151, was collected before the residue in the distilling flask became colored and viscous. final. Calcd. for 012Hl6: C, 89.95; H, 10.06. Found: C, 90.22; H, 9.76. The infrared spectrum had absorption band at 1018 cm.-1, for the cyclopropane ring, absorption bands at 1446, 1588, 1568, 1209, and 1186 cm."1 for the C(CH5)2 and the characteristic spectrum for monosubstituted benzene in the 5 to 6‘p.region and the strong 1 absorption bands at 699 cm.-1 and 760 cm.- Ethyl l-Phenylethylidene Cyanoacetate C75 ON I ©_ c : 000202145 The procedure of COPCv.E£.El° (40) was followed. Twenty-eight and five-tenths grams (0.25 mole) of ethyl cyanoacetate, 50 g. (0.25 mole) of acetOphenone, 50 m1. of benzene, 12 g. (0.2 mole) of acetic 55- acid and 5.85 g. (0.05 mole) of ammonium acetate were placed in a 500 ml. round-bottomed flask equipped with a constant water remover and reflux condenser. The mixture was refluxed for twelve hours. Eight milliliters (0.5 mole) of water was removed. The mixture was cooled and washed with three 50 ml. portions of water. The combined aqueous extracts were extracted with two 50 ml. portions of benzene. The combined organic extracts were dried over sodium sulfate, the solvent removed, and the residue distilled.in‘zggug. Nine and two-tenths grams of a mixture of starting materials, b.p. 940-1540 at 15 mm., was recovered. Twenty-six grams (48.5%) of ethyl l-phenylethylidene cyanoacetate, b.p. 1570-140o at 1.9 mm., was obtained. Ten grams of residue remained. Cepe, gt 31. (M3) report the boiling point is 1560-157o at 2 mm. The experiment was repeated using twice the quantities as described above. Forty-seven grams (44%) of product, b.p. 1570-140o at 2.2 mm., n35 1.5480 was obtained. Reaction of Acetoghenone and Ethvl Malonate The general procedure of Cope, gt al. (40) was followed. Forty grams (0.25 mole) of ethyl malonate, 50 g. (0.25 mole) of acetOphenone, 50 ml. of benzene, and 5.85 g. of ammonium acetate were placed in a 500 ml. round-bottomed flask equipped with reflux condenser and constant water remover. The mixture was refluxed for 15 hours. Three and three-tenths milliliters (0.18 mole) of water was removed. The mixture was cooled and extracted with three 50 m1. portions of water. The combined 56. aqueous layers were extracted with two 25 ml. portions of benzene. The combined organic extracts were dried over sodium sulfate, the solvent removed, and the residue distilled 33.13332. Fifty-three grams of a mixture of acetOphenone and ethyl malonate, b.p. 95°- 1000 at 20 mm. was recovered. Six and two-tenths grams of a yellow liquid, b.p. 1A0°~17o° at 1.8 mm., n35 1.58014 was obtained. Two and six-tenths grams of residue remained. Reaction of Ethyl l-Phenylethylidene Cyanoacetate and Ethyl Alcohol Method 1. Twenty-six grams (0.12 mole ) of ethyl l-phenylethy- lidene cyanoacetate, 55.2 g. of absolute ethyl alcohol and 12.5 g. (0.12 mole) of sulfuric acid were placed in a 250 m1. round-bottomed flask equipped with a water cooled condenser. The mixture was heated in an oil bath at 1500 to 1550 for three hours. The excess ethyl alcohol was distilled and the residue poured into 150 ml. of water. The mixture was extracted with four 50 ml. portions of ether. The combined ether extracts were dried over sodium sulfate, the solvent removed, and the residue distilled 12.13332. Four grams of material, b.p. 1500-156o at 1.8 mm., n35 1.5588, was obtained. Fourteen and one-half grams (56%) of starting material, b.p. 156°- 158° at 1.8 mm., n35 1.5478 was recovered. Two grams of a residue remained which was hold-up in the distillation apparatus. Method 2. Fourteen grams (0.065 mole) of ethyl l-phenylethyli- dens cyanoacetate, 5.5 g. (0.065 mole) of sulfuric acid and 50 g. (0.65 mole) of absolute ethyl alcohol were placed in a pyrex tube. The tube was sealed and heated at 1500 to 1400 for three hours. 57. The tube was cooled, opened, and the contents washed out with ethyl alcohol. The excess ethyl alcohol was distilled and the resi- due poured into 100 m1. of water. The mixture was extracted with three 50 m1. portions of benzene. The combined benzene extracts were dried over sodium sulfate, the solvent removed, and the resi- due distilled through the semi-micro distillation apparatus 22.12229, The following fractions were obtained: fraction 1, b.p. 600-65o at 1.8 mm., n35 1.4845, 1 g.; fraction 2, b.p. 650—1450 at 1.8 mm.,“ n35 1.5582, 2.7 g.; fraction 5, b.p. 1450-164o at 1.8-mm., n35 1.5460, 6.2 g. An elemental analysis of fraction 5 indicated nitro- gen was present. The refractive index of ethyl l-phenylethylidene cyanoacetate is 1.5480. Consequently fraction 5 appeared to be mainly starting material. DISCUSSION In 1928 Bruylants and Dewael (7) reported the formation of l- chloro-4—methy1—5-pentene from dimethylcyc10pr0pylcarbinol and hydrochloric acid. The 'proof‘ of structure of the chloroblefin, as shown below, involved the formation of the acetate followed by hydrolysis to l-hydroxy-4—methy1-5-pentene, which had previously been prepared by Van Aerde (41). OH I H01 cs\2 — EH — q — 035 ———> (Ch§)ZC=CnCH2CH201 CH2 CH5 KOAc AcOH a . (CH§)2C;CE10H20H20H 4—3— (CH5)2c=CIKCH20H20Ac KOH Although Van Aerde (41) prepared l-chloro-4—methyl-5—pentene by a different procedure, as shown in the following sequence of reactions, ' u -—+ Cl CH CN Cl CH 00 c ' Cl(Cle)5Br + KCN ( 2)§ -——> ( 2)5 2 2H5 CH5MgX ClCH2CIi201tC(CH5)2$ 01(CH2)50(0H)(0H5)2 he obtained the unsaturated alcohol from the chloroblefin by the same sequence of reactions used by Bruylants and Dewael (7). Thus, this does not constitute a rigorous proof of structure of the compounds involved. Bruylants and Dewael (7) and later Favorskaya and Fridman (8) reported that hydrolysis of l-chloro—4-methyl—5—pentene gave dimethylcyc10pr0pylcarbinol. 59. The identity of the hydrolysis product was based on a comparison of physical prOperties, such as, index of refraction and boiling point. In order to establish more conclusively the structures of these compounds, the reactions were reinvestigated, with the aid of the infrared absorption spectra. Dimethylcyclopropylcarbinol was pre- pared by the reaction of methyl magnesium iodide with methyl cyclo- prOpyl ketone. Its infrared absorption spectrum1 (see plate 1.) o o H KOH H ClCHZCHZCHZCCH5 ~——+ CH\2 ——/cd-c-CH3 CH2 . ., CH Mgl 5 as: V ‘3“ CICHZCHZCH-c(cs5)2 __....__.. CH\2 -——gH-0-CH5 -1 2 . indicated that the cyc10propane ring (1019 cm. ) and the tertiary - -1 . ‘ _ hydroxyl group (1150 cm. 1 and 1575 cm. )5 were present. Dimethyl cyclOpropylcarbinol was converted to 1-chloro-4-methy1-5-pentene with hydrochloric acid. The structure of the chloroolefin was sup- Ported by the infrared absorption spectrum (see plate 2.) with bands -1 - -1 ,- 1'} ( . for at 1678 cm. 1 and 854 cm. for the R20=Ch R and at 718 an ' '. 'th s ueous C-Cl.5 The chlorodlefin was hydrolyzed by reflux1rg w1 q —_- 2 . 1 The assignment of absorption bands were made from Bellamy (4 ) 60. IahmosaoHozeHhficaan mo 3.30on canvases“: «6.3th w. .5 Rod soofiosfi See .335 35er O. _ o F r 0 p . H Pecan 9.08.! 8. :thJgt’ C L r _ : .IOO . d jT‘ 80m d‘ u.‘ «1J5 4‘4 14 «1 83 7 to 5:33.... 61. V. .88 30.0 $083.39 :00 .sdcsv 0:9an ImaahnvofilqlougnouH ho goomm soavmhoonas counts; 0 Nu _ O.— . L F “-0 F F L . N “Fagin mzocgfl 2. 1h¢2m4w>d3 v “ Tom 100. —“ Id. l1 144n|41dd11— GOO GOO. DON. 00o. OOON 000' 7.3 Sausage 62. potassium carbonate, and the infrared absorption spectrwm of the product was identical with that of a known sample of dimethylcyclo- propylcarbinol. Thus, the rearrangements in the reaction of hydro- chloric acid with dimethylcyclopropylcarbinol and the hydrolysis of 1-chloro-4-methyl-5-pentene were confirmed. .Several attempts were made to prepare dimethylcyclOpropyl- carbinyl chloride from the alcohol. Experimental conditions were used which had previously been successful in preventing racemization or isomerization in preparing alkyl halides from the corresponding alcohols. Thus Gerrard (17) had found that active 2-octanol was converted to the chloride without loss of Optical activity using phosphorus pentachloride at low temperatures. Consequently, the reaction apparently did not proceed yig_a carbonium ion intermediate which would have given racemization. Dimethylcyc10pr0pylcarbinol, however, under the same conditions, gave no reaction (starting material recovered) or rearranged product (1—chloro—4-methyl-5- pentene). Gilman and Harris (18) used thionyl chloride and pyridine in chloroform in preparing cinnamyl chloride from cinnamyl alcohol. Other reagents, such as hydrochloric acid, gave an unsatisfactory product. Using the cyclOprOpylcarbinol, however, rearranged pro- duct or recovered alcohol were obtained. Hatch and Nesbitt (16) found that gig or trans-crotyl alcohol with phosphorus trichloride and pyridine gave respectively gig or igggg-crotyl chloride. By using these conditions, isomerization was avoided. The reaction of dimethylcycloprOpylcarbinol under 55. identical conditions, however, gave iSOprOpenylcyCIOpropane and recovered alcohol. In as much as the hydrolysis of l-chloro—4-methyl-5-pentene involved rearrangement from a primary chl ride to a tertiary alcohol, it appeared that this chloroolefin might be a potential source of a tertiary carbonium ion, or something akin to one. In order to deter- mine whether this was indeed the case, the uncatalyzed reaction of l-chloro-4-methyl-5-pentene with phenol was examined. It has pre- viously been shown (9) that tertiary alkyl halides alkylate the aromatic nucleus of phenols without the usual Friedel—Crafts type of catalyst; primary halides, on the other hand, unless unusually reactive (such as allyl or benzyl) do not give this reaction. The anticipated product was ErdimethylcyclOpropylcarbinyl phenol, but as shall be seen below, the reaction took a rather different course. When the chloroSlefin was heated with phenol at 1500 in a molar ratio of one to four, hydrOgen chloride was evolved, indicat- ing that a reaction occurred. The chloroolefin also reacted with peeresol at approximately the same rate as with phenol. Under identical conditions, l-chlorohexane and phenol did not react. Consequently, the carbon-carbon double in l-chloro-4—methyl~5- pentene must have provided a driving force in the alkylation. The product from the alkylation of phenol with l—chloro-4— methyl-5~pentene was investigated in detail. The reaction mixture was separated into a neutral fraction and a fraction which was soluble in 20% alkali. A crystalline compound, m.p. 470-480, 64. was isolated from the neutral product in 16% yield. This substance will be referred to as "A" for the remainder of the discussion. Another crystalline product, m.p. 1150-1140, was isolated from the alkali-soluble (phenolic) fraction in 29% yield. It will be referred to as “3" for the remainder of the discussion. In addi- tion, high boiling viscous liquids were obtained which were not further characterized. Neutral Produgt "A" "A" analyzed for 0125160 which corresponded to a monoalkylation product, as, for example CSH5OC6H11° An analysis of the infrared absorption spectrum (see plate 5.) indicated that the following groups or type of substitution might be present: C(CH5)21 1582, 1568, 1448, 1205, 1189 cm.“-1 Aromatic ether2 1285, 1226 cm..-1 _(3_r__t_1*_1_g~-disubstitutionfi’I4 1980, 1945, 1910, 751 cm.-1 The absence of a strong band at 700 cm...1 also supports_g£tgg- disubstitution on the benzene ring.5 The ultraviolet absorption spectrum of "A" (see plate 4.), 1 Bellamy, Chp. 2. 2 _Ibid., p. 102. 5 Ibid., pp. 65, 66. 4 These bands were obtained from the infrared absorption spec- trum in mineral oil mull, which was made available by Dr. g L. Johnson, Upjohn Company, Kalamazoo, Michigan. The 751 cm. absorp- tion band was obtained using carbon disulfide as the solvent for I! ‘3'. 65. .5 m6 oeofiosfi Soc .8333 ooflofisofioa senses 5” .4. vosvob— Hana—.62 mo goomm #0330094 “.03th .m as; mzozoi 2. 52.3343 o o J. _ N». _ 0.. p o. . _ p _ _ b O o. 9 . g s x on v. I. _ , o. w w 18 m S Y oo 5 O N _ is. _ loo _ Fa IOO co. — — — 1 .— d 4 d 4 d 4 d — d d d d d1 d J u q — of. con com 80. 08. con. 88 33 7:0 55:35 >lr-IU-‘Llll I 7.3 x Io’4M t-BUTYL PHENYL ETHER 0.4— 2 4.5x 10'4M “A“ CYCLOHEXANE SOLVENT 0.3— t (7, \ Z ‘3 2 3’ 20.2" I .— Q O 0.: — ° ' l l I so 250 256 262 268 274 2 A in m mm 4. ULTRAVIOLET ABSORPTION SPECTRUM * OF NEUTRAL PRODUCT 67. however, was comparable to that of t-butyl phenyl ether, which indicated that "A" might be a simple phenyl alkyl ether. Three structures of this type appeared possible since the ion from the homoallylic system of l-chloro—4—methy1-5-pentene has three contribut- ing forms. CH —— CH 2 2 \ . / ,. _ Td Cn2 CH2 1 ca2cnzcs=c( cs5).2 CPI;— C—CH5 cs —- C(Cflj)2 o o o I \ / I II III Neutral product "A" resisted hydrOgenation under conditions Which normally caused reduction of the carbon-carbon double bond. Furthermore, there was no evidence for the carbon-carbon double I! ll bond in the infrared spectrum. Consequently, structure I for A was doubtful. Nevertheless, an authentic sample of 5—phenoxy-2- - he methyl-2-pentene (I) was prepared and its structure proven by t following sequence of reactions: K2005 68. C6H50H-L(CH5)2C=CHCH20H201 —————9' C5H5OCH20H20H=C(CH5)2 Acetone I HBr H2’ Pt 06H50H1-(CH5)ZCHCHZCHZCHZBr 05H5OC(CH5)5 conversion to the ether. Larger amounts of sulfuric acid gave alkylated phenols. At 50°,‘trbutyl phenyl ether in benzene solution was cleaved rapidly by hydrogen chloride. Neutral product "A“, by refluxing with acetic acid and hydrobromic acid, gave a mixture of phenol and another alkylated phenol, "C". "C" will be discussed later. "A" was soluble in concentrated sulfuric acid and could be recovered from it unchanged, in direct contrast to t—butyl phenyl ether. "A“ was also thermally stable; after refluxing at 252° for three and one-half hours, "A" was recovered unchanged. Under these conditions tfbutyl phenyl ether rearranges to petrbutylphenol (45). Thus, by comparing the chemical prOperties of "A" with tfbutyl phenyl ether, structure II was eliminated. Structure III remains as a possibility for "A". As in the case of neOpentyl compounds, a difficult cleavage would be predicted. Once the cleavage had occurred the active carbonium ion formed would be expected to realkylate the phenol. Although not eliminated con- clusively by chemical evidence, it should be emphasized that III is | v 70- inconsistent with the infrared spectrum of "A” which indicates grthg—disubstitution. Further chemical evidence antagonistic to III is given below. Among the possible structures of "A" involving patho— disubstitution, the most likely would be the following: 0 0 0. saw a» a) cs(cs 5)2 (CH5)2 Iv v VI When "A" was dissolved in sulfuric acid, a red color typical of chromans was observed. Also, the chroman structures (IV and V) would be consistent with QEEEQ-disubstitution indicated by the infra- red spectrum. Accordingly 2~is0propylchroman was prepared by an unambiguous route. The ultraviolet absorption spectrum of OH NaOH OH CHO ---’ y: u C CH 0005(03 )2 CH cuco H(CH5)2 5 3 Pt,H2 0H 0 Zn 03(035)2 ‘g___ "CH20HQCOCH(CH5)2 H230, IV 71- 2-isopr0pylchroman (see plate 5.), with bands at 274.5 my and 284 my, indicated that “A" did not have the chroman structure (IV and V). The ultraviolet absorption spectrum of 2-i30pr0pylchroman was com- patible with 2,2-dimethylchroman which absorbs at 278 my and 284 mp (45)- Further chemical evidence is given below for eliminating the chroman structure. Structure VI remains as a possible structure of "A". The infra- red spectrum.of "A" is compatible with the groups present; i.e., the C-(CH5)2 group, an aromatic ether, and ortho-disubstitution on the benzene ring. The predicted chemical prOperties are also consistent. The ether linkage would be resistant to cleavage, such as, a primary alkyl phenyl ether. The cleavage of structure III could occur with complete loss of the alkyl group from the phenyl ring to give phenol, which was found in the cleavage of "A". Instances are found in the literature where tertiary alkyl groups have been removed by acids, as in the nitration of l,1,2-trimethyl-5-indanol (4h). Structure VI appears to be the most probable. The most com- pelling evidence for structure VI is the formation of "A" from 5-phenoxy-2-methyl-2—pentene when the latter was treated with a few drops of concentrated sulfuric acid. This can best be formulated as follows: 72. 0.7 0.6 — 0.5 - >. ':. m 0.4 — Z U Q .l < 9 o.3- p. O. o 0.2 ~— 0.: 3.9 x Io‘4M 2-ISOPROPYLCHROMAN CYCLOHEXANE SOLVENT O L J 1 I 250 253 266 278 282 A in mu 290 mm 5. ULTRAVIOLET ABSORPTION SPECTRUM OF 2- ISOPROPYLCHROMAN 75- | + H «-——er 1 ’r I 5 2 , .. .. . .fio CH201~120H=C(CH§)2 + I \ OCEZCHZancr‘AZC(C“§)2 . + / (“5’2 VI The tertiary alkyl ion formed by protonation of C5 in the first step would be very reactive and alkylation would be anticipated. The fact that only "A" was isolated also indicates that there was not an initial cleavage and then realkylation. Furthermore, l-phenoxy—h— methylpentane (isohexyl phenyl ether) was not cleaved under identical conditions; hence, the formation of "A" from I proceeds intramolecu- larly. In order to form h—igopropylchroman (V) from I: dOUbthI reverse addition of sulfuric acid to the double bond would be required. The formation of structure III from I by sulfuric acid seems very improbable, especially, considering that cleavage of the ether linkage does not occur. The possible exception for structure V1 is the ultraviolet absorpt on spectrur. The ultraviolet absorption spectrum can be rationalized for this type of structure in the following manner: 2-methylcounaran absorbs at 281 my and 259 my (45); Z-iSOprOpylchroman 74. absorbs at 274.5 my and 264 mp (see plate 5); 2,2-dimethylchroman absorbs at 278 my and 284 mp (45); and Erbutyl phenyl ether absorbs at 254 my and 270 niu (see plate 4). The absorption bands are shifted prOgressively to shorter wavelengths as the heterocyclic ring is increased from five in coumaran , to six in chroman, to the cmnplete Open chain in trbutyl phenyl ether. The seven membered ring in structure VI would then be expected to have absorption bands between those of t—butyl phenyl ether and chroman. "A" absorbs at 266 mp and 271.5 mp which is in the predicted range for structure VI. From the chemical and spectral evidence it seems very probable that VI is the correct structure for "A“. Structure VI could also explain the formation of an alkylated phenol, "C", from "A". The ultraviolet absorption spectrum of "C" (see plate 5) has bands at 279 my (broad band) and 288 mp which is typical of a p—alkylated phenol or S-tetralol, the latter of which has absorption bands at 279 mu, 281.5 my, and 289 mp (40). Thus one o 4 ' . ~\ 68- - possible structure for "3" which could be postulated from the r c ‘ - ' —‘ ' . ~ 1 mic acid tlon of structure VI in refIUXlng acetic acid and hydrobro is shown below. OH (CH§)2 \ 1:: / OH :1; - @j \ C(CH5)2CHZCH20H2+ (cs5)2 /_,* HO ‘?//’ VI (cap2 75- The initial cleava:e of VI is followed by alkylation in the meta ‘d position. The tertiary alkyl group on the ortho position could then rearrange to the para position giving the 6-tetralol type of struc— ture. This mechanism is not unique for the formation of an alkylated phenol from "A"; the tertiary alkyl group could possibly be displaced prior to the cleavage of the ether linkage. On the whole, this series of transformations is not too satisfactory. The structure of "C“ is not established and it requires further work. Phenolic Product 1B: The phenolic product "B" analyzed for C12H16O which corresponded to monoalkylation of phenol with the chloroolefin. The neutraliza- tion equivalent of the phenoxyacetic acid derivative, and the ele- mental analyses of the g3-naphthyl urethan, benzoate, and methyl . II N ' ' ' was a mono- ether derivatives of "B" gave further evidence tnat B alkylated phenol, such as, 06H1106H4OH' The ultraviolet absorption spectrum of "B" (see plate 6) was similar to that normally obtained from ortho or meta alkylated Phenols (see Table IV). The position of the absorption bands were . h' considerably different from that of a.pfalkylated phenol T is re, pfdimethylcycIOpropyl- seems to eliminate the anticipated structu carbinylphenol. H O mi—C“CH 51H 5 /C\ (ct—”21"? IF, 2. Mi.9‘%..~am~ d. .8". in OPTICAL DENSITY 76. 0.7 0.6- 0.5- 2 0.4- o.3~ / 0.2- / 4.I XIo’4M "s" 0'” 2 Is.XIo‘4M “c" CYCLOHEXANE SOLVENT o I I I I 260 266 272 273 284 A In m» PLATE 6. ULTRAVIOLET ABSORPTION SPECTRA 0F PHENOLIC PRODUCTS 290 77. TABLE IV. ULTRAVIOLET ABSORPTION BANDS OF VARIOUS ALKYLATED PHENOLS. _ngpound Absorption bands (mu) Referengg Ig-ethylphenol 272 276 (46) grcresol 272 278 (46) gftrbutyphenol 271 278 (47) 'm-ethylphenol 272 279 (46) ,gecresoi 272 279 (A6) ‘pfcresol 279 287 (A6) ‘pet-butylphenol 277 285 (A7) .p-ethylphenol 278 285 (46) “B“ 272 279 Coggeshall and Glessner (45) reported for various alkylated Phenols that a shift of the ultraviolet absorption spectrum to higher wavelengths was found for unhindered phenols in 0.1 M sodium hydroxide solutions. They included ortho-substituted phenols, such 88: 2,5-dimethylphenol in the class of unhindered phenols. The Ultraviolet absorption spectrum of "B" in 0.1 M sodium hydroxide II II solution1 showed such a shift to higher wave lengths; hence, B was either unsubstituted in the ortho position or the group, if Present, did not sterically hinder the hydroxyl group. An ortho- Subetituted phenol structure for "B" appeared quite improbable, A ion spectrum of "B" in 0.1 M sodium 1 The ultraviolet absorpt ard Oil hydroxide solution was determined by Dr. R. B. Hannan, Stand Company of Indiana, Whiting, Indiana. 78. since the possible alkyl groups would have six carbon atom, branched chain structures. Thus, from the ultraviolet spectrum "B" appeared to be a meta or an ortho substituted phenol (which was not hindered), or possibly alkylated in both positions. An analysis of the infrared absorption spectrum (see plate 7,8) was complicated by the large number of absorption bands. The follow- ing groups were indicated: 1 , -1 phenolic C-OH 5600, 1234 cm. -i C(CH5)22 1462, 1442, 1589, 1568 cm. 5 The 5,u to 5 p.region in the mineral oil mull absorption spectrum showed 1,} or 1,2,5 substitution on the benzene ring. Young, gt al. (49) have shown that a characteristic absorption pattern is obtained in this region for variously substituted benzene rings. "B" absorbed at 5.2, 5.4, 5.7, 6.0 p with approximately equal intensities. 1,5— substituted benzene compounds show bands at 5.2, 5.4, 5.7 and a weak band at 5.8‘p. 1,2,5-Substituted benzene compounds have bands at 5.2, 5-4: 5.5, and 6.0‘p. Other structures have different patterns. The position of absorption varies to a certain extent but the overall Pattern, including relative intensities, remains independent of the tYPe Of groups on the benzene ring. *— l Bellamy, p. 84. 2 Ibid., Chps 2. "B" in mineral oil mull The infrared absorption spectrum Of Kalamazoo, Michigan. was supplied by Dr. J. L. Johnson, Upjohn Company, ‘ 79. .as he possesses. Zoo 53.338 ceases 5 .9. so goose 339322 33th .N. mafia Q. N. m:0¢0.1 2. 1h u:u..u>¢’ C p _ . v-CD Ion nu .l a ocv oo. . a 4 4 q ddqfi OON. 000. 89 720 52302.. 80. 033306.309 £09.80 s.“ am. He goon» coavnuoupd unsung” N. O. .3 no .3635. 2.6 --O '0 .w my; $205!! 2. thoquu>C3 a _ u. 0. ON Gnu» m Ila" N loo“ 5 Ice 5 N th loo [on d A OOON d 00. dddddddd— 89 710 52.335. 81. 1,5- and 1,2,5-substitution1 was also supported by the bands at 717 cm.-1 and 778 cm."1 Unfortunately, the phenolic C-O absorbs in the 1200-1500 cm.”1 region eliminating use of this region for assignment of type of substitution. There was no band near 1025 cm.-1, which would have been evidence for the cycIOpropane ring2. Also, there was no sharp band present for the carbonrcarbon double bond5 at 1680-1520 cm.-1 Hence, from the ultraviolet and infrared absorption spectra one would conclude that "B" was a phenol which was either meta- alkylated, or ortho-meta dialkylated, with the latter formulation fitting the spectra somewhat more closely than the former. Although it seemed most unusual that phenol should have been mono-alkylated in the meta position, our initial efforts were directed toward . . . . - th' e of prov1ng or eliminating structures of this type. At .19 stag the problem, the interpretation of the infrared spectrum in detail, as above, was not possible. For a 1,5 disubstituted benzene ring the following structures . . d 0f "3" were possible. The three structures of R in VII are derive OH VIIa a .: -CHZCHZCHIC(CH3)2 :0 \ VIIb R CH2 -— cm ——cs»cn C( 92 \ /2 as l\ 8110 -CI~: —- 3mg), Ch'2—- Ch2 l Bellamy, p. 66. 2 Ibid., p. 28. 5 Ibid., p. 520 82. from the three contributing forms of the homoallylic ion of l-chloro— 4-methyl-5-pentene. Certain of the structures postulated for "B" can be tentatively eliminated from the absence of certain bands in the infrared absorption spectrum. Thus, the absence of a medium intensity absorption band from 1680-1520 cm..-1 indicated the absence of a carbon-carbon double1 bond, eliminating structure VIIa. There was no evidence for the cyclOpropane ring2 by the absence of a band near 1025 cm.-1 which should probably have been present if VIIb were the correct structure. To further verify this, dimethyl- cycloprOpylcarbinylbenzene was prepared by methods previously used to prepare alkyl cycloprOpanes (57, 59), and its infrared abSOTPtiOH spectrum was analyzed (see Plate 9)- CgHSMgBr + (CH5)20:C(00202H5)2__,.06350(Ch5)2‘05(00202h5)2 o 1' ' \ Llfi d4 PBr 06h50(Ch5)Ch(CE25r)2 ,. 5 05n50(055)20n(3n20b)2 I? z/TT)“/' Zn ‘ Si. 601 Gas cs . “ 5 055 on, I /’ ca_—c—cs L} D I .. \i. an One !_ - p d " orted by the inirare The structure of the product was supp ‘ -1 . ' ' ‘ * 017 cm. for the absorption spectrum with absorption bands ab 1 . A J-— 1 881183133 p. 520 2 Ibid., p. 2&0 Ch. a}. .88 Hmo.o amoexoanv Haoo .Avdocv onownonahcapueo Iahmoumoaohoahgvcaan Mo souvoomm coavahoep< conduMGH .m me<4m atop-0.1 z. Ihazudw‘i’ o v C». _ Np. _ O.— _ O— p _ _ _ _ b O 0. ON on um [- Ioew w 9 - co m 0 N I05 I00 I00 . 00. u A — — 1 fl ‘ 4 _ d a q a — q d a a 4 d 4 . ‘— ot. 000 8a 000 _ CON. 000 . 80m 000' 7.6 55:35 84. ' rm -1 cyCIOprOpane ring, bands at 1445, 1560, 1558 cm. for C(Ghi)9 and the pattern in the 5 p to 6.P region was similar to that found by Young, at al. (49) for monosubstituted benzene ring. Dimethyl- cyclopropylcarbinylbenzene had four typical bands at 5.15, 5.55, 5.45, and 5.78‘p.whieh were similar to those for a monosubstituted benzene D " I 9 1 ‘ I O . ring. AODOSUbStIIUthh was also further verified by the absorption 1 J- K -1 / , -1 \ - sands ab 76) cm. and 599 cm. The presence of a sharp cyclopropyl . -l . . . . . sand at 1317 cm. in dimethylcycloprOpylcarbinylbenzene indicated . . -1 . if VIIo were the correct structure, the 1017 cm. snould have appeared in the spectrum of "B". Oxidation of "B" with potassium permanganate was attempted several times following a procedure (27) which had previously been used successfully on monoalkylated phenols. The purpose was to OH | KNnOg / ____,— R“COZH + CO2 + H20 .\\\ __ R obtain the alkyl group as an acid which could be converted to an - m, ‘ r . Unfortunatel amide and evencually characterise the alkyl group Y n distillation under reduced pres- c acid, (CE-{5)ZCL-ICIE20H2CH20 JZH, the "acid" obtained decomposed o . o s ' 1 ' sures; yet monocarboxylic aCids as isomyiacetl ' ' ‘ ' II' 0- can be distilled at atmospheric pressures without deceip eition. 1 578118357, p. 650 .E $0.0 :3on Soc .335 .9. no 85a :32: on... no 5533 Sfifioofi 3.8th o _ o. _ _ . --O .04. Pair» m20¢0=4 :- 1h02m4u>13 v p _ _ or 000 00m 000. OON. 000. — a d deqduq— 88 83 7:0 55:35 85. The methyl ether of "B" (infrared absorption spectrum given in Plate 10) was then oxidized with potassium permanganate to determine the position of alkylation. It was hoped to isolate a anethoxybenzoic acid; however, the mixture isolated was a dark oil which did not solidify. If VII were the correct structure, an R group as in VIIb would not be expected to give a benzoic acid ’ OCH KM O R CO H because of the tertiary alkyl group adjacent to the ring. VIIa and VIIc would be expected to give the acid more easily. Additional structures of "B" will be postulated later which also would not be anticipated to oxidize completely because of a tertiary alkyl group adjacent to the benzene ring. further experiment designed to show the alkylation of "B" was not para, was the attempted nitrosation of "B". The experimental procedures used (28, 29) gave good results with mfcresol. Nitrosa- tion of metrbutylphenol using the same conditions, however, gave inconclusive results. A dark colored material was obtained. A solid product was obtained from the nitrosation of "B"; the analysis of the nitrosated product gave a very low analysis for nitrOgen and high analysis for carbon. Thus "8" acted similar to Egg-butylphenol in not giving the appropriate nitrosOphenol. The unreactivity may be attributed to the steric hindrance of a large group present in the meta position. 87. In summary, then, oxidation and nitrosation experiments are not consistent with structures VIIa or VIIc, but indicate that a large group may be present in the position meta to the hydroxyl. .Other structures for "B" were possible which could fit the spectral and chemical evidence; i.e., the trisubstituted benzene ring. Any trisubstituted benzene ring would require that group occupying the ortho position to the hydroxyl group be small. 1,2,5- Trisubstituted benzene structures for "8" involved bicyclic struc- tures as VIII and IX. OH 0; CH 5 CH CH 5 3 VIII IX Both structures VIII and IX were compatible with the infrared absorption spectrum of "3", with the group C(CH5)2 present and 1,2,5 trisubstitution. The ultraviolet absorption spectrum of "B" was similar to 5-tetralol which absorbs at 271, 272 and 279 mp (46), but dissimilar to A—indanoi which absorbs at 259, 270 and 276 hp (46). "B" absorbed at 272 my and 279 mu. Either VIII and IX were also com- patible with the ultraviolet absorption spectrum of "B" in alkaline solution on the condition that position 4 in VIII and 5 in IX were unsubstituted. The methylene group should offer no more and pro- bably less hindrance than the methyl group in 2,6-dimethylphenol. 88. Structures VIII and IX are also consistent with the chemical evidence. The relative ease of formation of derivatives of "B", such as the benzoate, indicate that the phenolic hydroxyl group was unhindered. The tertiary alkyl group would prevent oxidation of the methyl ether of "B" to 5-methoxyphthalic acid. The experimental conditions used in the oxidation of "B" itself were not suited to the isolation of a dicarboxylic acid. Dicarboxylic acids, such as adipic acid, are not readily extracted from aqueous solutions by benzene. The meta tertiary alkyl group would also be consistent with the lack of formation of a nitroso derivative from "B". Further- more, the bicyclic structure would eliminate the need for a mechanism to explain meta substitution in phenol, which normally substitutes in the ortho or para positions. The preparation of 5—(g-hydroxyphenyl)-2-methy1-2-pentene and the corresponding para isomer was attempted to see if they were intermediates in the formation of "A" and "8". CH CH 5 3 o o 0 o u I CdZCd-L-CC(CH§)2 Pt.H2 CH20HZCCH(CH5)2 -———-9- LiAlH i 4 CH5 0 00H5 OH , ._ l f \\i Cd2CH20H-C(CH§)2 -H2O ‘\\ CH2CH2CHCH(C“5)2 «——— I \x/ / | b 85? . Unfortunately, the dehydration of l-(grmethoxyphenyl)-4-methyl- 5-pentanol with sulfuric acid gave a mixture. The dehydration of l-(pfmethoxyphenyl)—4-methy1—5-pentanol using Whitmore's (54) modi— fication of the Tschugaeff reaction also gave a mixture. A better procedure for preparing 5-(g-methoxyphenyl)-2-methy1- 2-pentene would be by the dehydration of the tertiary alcohol, 5- (gfmethoxyphenyl-2-methyl-2-pentanol. CH 0H 05 Cu-Cr CHZ-CHZ-CHZOH CflchQCHgoH H ’ (CH ) so 2500, 100 atms. aq. KOH - err OCH5 cs‘ 6 3 OCH5 CH -CH -CH - - a 2 2 2. (UMs ,,,. CH5 _‘____ Cd20n2Ch2Br (2) Acetone H OH OCn; ' \\\ CHZCH23320(CH5)2 HBr t20H203=C(0 5)2 /’ AcOH This proposed series of reactions leading to the tertiary alcohol starts with the reduction of coumarin. Unfortunately it was not possible to carry out this reduction because adequate hydrOgenation apparatus was not available. Phenolic Product "C“ “C" analyzed for 012H15O. The infrared absorption spectrum (see Plates 11 and 12) were very similar to “B" with the differences 9C. occurring from 1200 cm.-1 to the lower frequencies. The infrared absorption spectrum appears to support the same type of substitution on the benzene ring as "B". The ultraviolet absorption spectrum (see plate 5) indicates that "C" is a para substituted phenol with bands at 279 my and 268 mu. (Cf. with the p—alkylated phenols in Table IV). A 5,4-disubstituted phenol as shown in structures x1 and XII is possible. The ultraviolet absorption spectrum of "C" is more consistent with that of 5-tetralol (45) with absorption bands HO HO CH5 CH5 CH5 Ch5 XI XII at 279, 281.5 and 289 my than with 5—indanol which has absorption bands at 282 and 285 mp. Thus XI seems the more probable structure for "Cu . Since "G" was isolated in small quantities, no chemical degra- dation or reactions were attempted. It was hoped that the eventual determination of the structure of "B" would indicate the possible structure of "C". More of "C" will be available from the reaction of "A" with hydrobromic acid and acetic acid, since "A" can be made in larger quantities from 5—phenoxy-2-methyl-2-pentene and sulluric acid, than from the direct reaction of l-chloro-4—methyl-5—pentene With phenol. e 1. ‘ I The formation of compounds of structures similar to XI and XI They alkylated phenol have been reported by Bruson and Kroeger (50). 91. 63.3330 £09.30 5 so: no guwoomm :owvmuooes oeudumcH O. .sa To accesses. Zoo .2 my; m20¢91 2. Ik02w4w>d3 l—Q 2r _ m. _ ._. _ m m. d d 4 a d d d — 83 7.3 5:33.... 92. .5 m6 aaofiog :8 6382852. noose E .o. no 5383 couscous: soaaCsH .3 22.5 m20¢93 z. Ib02fl4fl>4§ v. N. _ H . a -—CD & u, & — — d1 — d 4 — J u 5 4 — J 4 d d d d a d ‘1— h 0 com 000. CON. 000. OOON 0000 7.3 55:85. 95- with 2,4-dimethyl-2,4—hexandiol, 2,4-dimethyl-2,4-dichlorohexane, and 2,4-dimethyl-2,4-hexadiene using aluminum chloride as a catalyst and in each case isolated the same alkylated phenol to which they gave the structure XIII (l,l,4,4-tetramethyl-5-tetralol). However, CH CH so 5 5 i C, CH5 h5 XIII the proof of structure was not rigorous. Bruson and Kroeger (50) also found that alkylation using sulfuric acid as the catalyst gave an isomeric alkylated phenol for which they postulated struc- ture XIV (l,l-dimethyl-5-isepropyl-5—indanol). HO CL(CE5)2 CH CH 5 5 XIV L _I _ . __ The products, then, of the reaction between l-Cnloro 4 methyl 1 with 5“Pentene and phenol are an ether of structure VI and a pheno the probable structure VIII. These are not the anticipated products, had the double bond participated in the reaction analOgously to its role in the formation dimethylcyc10pr0pylcarbinol from the chloroolefin. 9h. There is no doubt, however, that the f3,Y'—double bond has been effective in activating the primary carbon to chloride bond. The mechanism by which this activation occurs is not clear, and it requires further study. In addition to the need for more evidence on the structure of the products described in this thesis, it would also be advantageous to study the effect of structure of the chloro- olefin and the phenol on the course of the reaction. Other experi- ments with l,h-dich10ro-h-methylpentane, 5—chloro-2-methyl-2-pentanol, and 4—methyl-1,§—pentadiene and phenol might also be helpful. SUMMARY The rearrangement of dimethylcycloprOpylcarbinol with hydro- chloric acid, to l-chloro-h—methyl-fi-pentene, and the hydrolysis of the latter back to dimethylcyclOprOpylcarbinol was reinvestigated using infrared absorption spectra. The rearrangement and the assigned structures were confirmed. Several attempts were made to prepare dimethvlcycloprOpylcarbinyl chloride from the corresponding alcohol by methods which were known to produce alkyl halides from alcohols without rearrangement. These methods were unsuccessful; in each case, dimethylcyclopropylcarbinol either did not reset or the rearranged chloride, l-chloro-h—methyl-fi-pentene, was obtained. 0 l-Chloro—Q—m thyl—5-pentene, when heated with phenol at 150 , gave two isomeric crystalline products. One was an either to which structure VI was tentativelv assigned. The elemental analySis and infrared and ultraviolet absorption spectra were consistent With this structure. Furthermore, the ether was syntneSized from 5- phenoxy-Q—methyl-2-pentene, by treatment with concentrated sulfuric CH5 CH5 VI ' ‘ v ' for this ether aCid. A numaer of likely alternative structures . were examined and discarded. The second product was an a kylated phenol. The anticipated product of the reaction was p-dimethylcycloprOpylcarbinylphenol. Infrared and ultraviolet absorption spectra quickly demonstrated that the anticipated product was not obtained. A number of possible structures were considered, and the one which is most consistent with the chemical and physical evidence is 1,1-dimcthyl-5-tetralol OH \\ // l t CH CH 5 VIII 5 (structure VIII), but further work is necessary to establish this structure conclusively. When the ether, 5,5-dimethylhomochroman, was treated with hydro- bromic acid and glacial acetic acid, another isomeric phenol was obtained. The structure of this compound is not clear, but it prob- ably has alkyl substitution para to the hydroxyl group. During the course of these studies several new compounds were prepared. These compounds were: 2—i30pr0pylchroman, 5—phenoxy-2- methyl-Z-pentene, 5-(2-methoxyphenyl)-2-methy1-5-pentanol, 5-(2- methoxyphenyl)-2~methyl-§-pentanone, 5—(p-methoxyphenyl)-2-methyl- 5-pentanol, 5-(p—methoxyphenol )-2-methyl-5-pentanone and dimethyl— cyCIOprOpylcarbinylbenzene. Some reactions of t—butyl phenyl ether were also examined. 9. 10. 11. 12. 15. 20. 21. BIBLIOGRAPHY S. Winstein, H. V. Hess and R. E. Buckles, J. Am. Chem. Soc., 14,2795 (1942). D. J. Cram, ibid., 11, 5875 (1949). s. Winstein and s. Grunwald, ibid., §§, 556 (1945). C. W. Shoppee, Bull. soc. chim., O. 120 (1951). S. Winstein, B. K. Norse, E. Grunwald, K. Schreiber and J. Corse, J. Am. Chem. Soc., 13, 1115 (1952). s. Winstein and R. Adams, ibid., 19, 858 (1948). P. Bruylants and A. Dewael, Bull. Sci. Acad., Belg., (v), 139 140 (1928). T. A. Favorskaya and Sh. A. Fridman, J. Gen. Chem., (U.S.S.R.), .15, 421 (1945); C. A. 39, 4555 (1946). J. H. Simone and H. Hart, J. Am. Chem. Soc.,l§§, 1509 (1944). J. D. Roberts and R. H. Mazur,.ipgg.,‘15, 2509 (1951). J. D. Roberts and R. H. Mazur, ibid., 12, 5542 (1951). Org. Syntheses, 21, 75 (1951). R. Van Volkenburgh, K. Greenlee, J. Derfer and C. E. Boord, J. Am. Chem. Soc.,‘11, 172 (1949). C. G. Swain and H. B. Boyles,‘i§id.,‘12, 870 (1951). W. A. 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Bellamy, "The Infra-red Spectra of Complex Molecules," John Wiley and Sons, Inc., New York, 1954. R. A. Smith, J. Am. Chem. Soc., 55, 5718 (1955). J. B. Niederl, V. Niederl and S. Reznek, ibid., 8, 557 (1955). T. J. Webb, L. E. Smith, W. A. Bestedo, Jr., H. E. Ungnade, W. W. Prichard, H. H. Hochn, S. Hawzonek, J. W. Opie and F. L. R. A. Friedel and M. Orchin, "Ultraviolet Absorption Spectra of Aromatic Compounds," John Wiley and Sons, Inc., New York, 1951. H. Hart, J. Am. Chem. Soc.,'11, 1966 (1949). N. D. COgEeshall and A. S. Glessner, Jr., ibid., 11, 5150 (1949). C. N. Young, R. 8. Der Vall and H. Wright, Anal. Chem., 25, 709 (1991). H. A. Bruson and J. W. Kroeger, J. Am. Chem. Soc.,.§g, 55 (1940). Org. Syntheses, 22.2, 20 (1945). L. I. Smith and E. R. Roaier, J. Am. Chem. Soc., 15, 4048 (1951). L. I. Smith and E. R. Rosier, ibid., 75, 5842 (1951). VITA Charles Roe Wagner candidate for the degree of Doctor of Philosophy Dissertation: An Investigation of the Uncatalyzed Alkylation of Phenol with l-Chloro—4-methyl-5-pentene Outline of Studies Kajor subject: Organic Chemistry Minor subjects: Physical Chemistry, Inorganic Chemistry Hio;raphica1 Items Born, December 5, 1925, Olivet, South Dakota Undergraduate Studies, Augustana College, Sioux Falls, South Dakota, 1946-1947; South Dakota School of Mines and Technology, l947~1950 Graduate Studies, Michigan State College, 1950-1955 Member of Sigma Tau, Society of Sigma Xi, American Chemical Society CH EMISTRY IibefifiY JUN21 ’62 CHEMISTRY usmuw thesis e.2 Wagner, Chas. Roe Ph‘Do 1955 An investigation of the uncatalyz- ed alkylation of phenol with l-chloro-ll-melhyl-S-pentene. CHEMISTRY LIBRARY Thesis 0.2 Wagner. Charles Roe Ph.D. 1955 .lui \\\\ BH‘I‘Ilm IL ‘. ‘ I a. l Ila,