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SYNTHESIS and PROPERTIES of SOME ARALKYL Hymoperoxides

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SYNTHESIS and PROPERTIES of SOME ARALKYL Hymoperoxides SYNTHESIS AND PROPERTIES OF SOME ARALKYL HYmOPEROXIDES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By ARLO d / bCGGS, B.S., M.S. The Ohio State University 1954 Approved by: Department of Chemistry ACKNOWLEDGEMENT The author wishes to express sincere appreciation to Professor Cecil E. Boord for his advice and counsel during this investigation* Thanks also are due Dr. Kenneth W*. Greenlee for his continual interest and guidance and his cooperation in ex­ tending the facilities of the American Petroleum Institute Research Project 4-5* The financial support of this work by the Firestone Tire and Rubber Company is gratefully acknowledged* ii TABLE OF CONTENTS Page I. INTRODUCTION................................ 1 II. LITERATURE S URVEY ............... 2 III. STATEMENT OF THE PROBLEM.................... 10 IV. DISCUS5IŒ ........................... 11 A. Methods of Preparing Hydroperoxides .... 12 1. Preparation of hydroperoxides from alcohols ............. 12 a. a-methylbenzyl hydroperoxide ...... 12 b. benzyl hydroperoxide .......... l6 c. cinnamyl and a-phenylallyl hydroperoxides 17 d. 1,2,3,4-tetrahydro-l-naphthyl hydro­ peroxide ............ 22 e. a-indanyl hydroperoxide ........ 23 f. 0-, m- and p-methylbenzyl hydroperoxides 24 g. m- and p-methoxybenzyl hydroperoxides. 28 h. 1,1-diphenylmethyl hydroperoxide .... 31 i. 1,2-diphenylethyl hydroperoxide .... 32 j. 1-a-naphthyl- and l-J3-naphthylethyl hydroperoxides ........ 33 k. 1-styrylethyl hydroperoxide 35 1. 4-a-dimethylbenzyl and 4-methoxy-a- methylbenzyl hydroperoxides ...... 36 m. a-ethylbenzyl and a-ethyl-p-methylbenzyl hydroperoxides ....... ........ 36 n. a-n-propylbenzyl and a-isopropylbenzyl hydroperoxides .................... 37 0. a-2,5“trimethylbenzyl hydroperoxide . 37 2. Preparation of hydroperoxides from olefins 38 a. a-ethylbenzyl hydroperoxide ...... 38 b. a-ethyl-p-methylbenzyl hydroperoxide . * 39 c. 1,2,3,4-tetrahydro-l-naphthyl hydro­ peroxide ........... 40 d. a,a-dimethylbenzyl hydroperoxide .... 40 e. a-indanyl hydroperoxide ........ 40 f. 1-benzylethyl hydroperoxide ...... 41 B. Purification of Hydroperoxides ...... 41 1. Distillation ............ 41 iii TABLE OF CONTENTS Page a. isolation of pure a-methylbenzyl hydroperoxide •••••••••«•• 41 b. distillation of benzyl hydroperoxide • 43) c. distillations of miscellaneous hydro­ peroxides . 45 2. Salt formation 4-6 a. Hydroperoxides giving crystalline salts 46 b. Aqueous alkaline extraction as a means of increasing hydroperoxide purity 46 c. Effect of solvent on salt formation 47 d. Composition of the crude concentrate and its effect on salt formation 48 e* Fractional salt formation as a means of purifying hydroperoxides • • « « 48 3. Recrystallization of hydroperoxides 50 a, 1,2,3,4-tetrahydro-l-naphthyl hydro peroxide b)• 1" ,1' -diphenylmethyl■ hydroperoxide o c 1,2-diphenylethyl hydroperoxide • I C. Identification and Characterization of Hydroperoxides ................... 50 1* Physical properties 50 a. Refractive index and boiling point 50 b. Melting point , . « c. Spectra ••••••• e 2. Degradative methods 52 a. Elemental analyses......... • • be Decomposition of hydroperoxides • 1) Acid catalyzed decomposition of hydroperoxides e # e e . 52 2) Base catalyzed decomposition of hydroperoxides 53 3) Thermal decomposition of hydro­ peroxides eeeeeeeeee 55 Ce Determination of purity of hydroper oxides .......... .. 55 IV TABLE OF CONTENTS Page 1) Chromatography ••••«•••••• 55 2) lodometric titration •«••••••• 5° V. EXPERIMENTAL A. General Information................... 58 1» Apparatus and conditions ...... 58 2. Miscellaneous materials .......... 59 3* Preparation of olefins .......... 60 4. Preparation of alcohols ...... 6l B. Preparation of Hydroperoxides from Alcohols 65 1. General procedures ......... 65 2. Some typical experiments ....... 68 a. benzyl hydroperoxide .......... 68 b. 0-, m-, and p-methylbenzyl hydro­ peroxides .......o ........ 69 c. a-methylbenzyl hydroperoxide ...... 72 d. 1,2,3,4-tetrahydro-l-naphthyl hydro­ peroxide ........ ............ 72 e. a-indanyl hydroperoxide ....... 74 f. 1,1-diphenylmethyl hydroperoxide .... 74 g. p-methoxy-a-methylbenzyl hydroperoxide . 77 h. cinnamyl and a-phenyl allyl hydroper­ oxides* ............. 77 io miscellaneous alcohols............. 80 C. Preparation of Hydroperoxides from Olefins 80 1. General procedures ...... ........ 80 2. Some typical experiments ......... 80 a. a-ethylbenzyl hydroperoxide ...... 80 b. a-ethyl-p-methylbenzyl hydroperoxide . 84 c. a,a-dimethylbenzyl hydroperoxide .... 86 d. 1-benzylethyl hydroperoxide .......... 88 e. a-indanyl hydroperoxide ........ 90 f. 1,2,3,4-tetrahydro-l-naphthyl hydro­ peroxide ............... 91 V TABLE OF CONTENTS Page D* Purification of Hydroperoxides 94 1. Distillation ...... 94 a. a-methylbenzyl hydroperoxide • • • 94 b. benzyl hydroperoxide ...... 98 c. miscellaneous distillations . « . « 100 2. Salt formation 101 a. General procedure . 101 b. Precipitation of hydroperoxides as sal 102 1 ) a-methylbenzyl hydroperoxide . • 102 2 ) l,2,3»4-tetrahydro-l-naphthyl hydroperoxide ......... 104 3 ) a-indanyl hydroperoxide ..... 106 4) miscellaneous hydroperoxides . 107 c. Alkaline extraction of hydroperoxides 108 1 ) benzyl hydroperoxide ...... 108 2 ) cinnamyl and a-phenylallyl hydro­ peroxides .............. 112 3 ) p-methylbenzyl hydroperoxide « . 4) p-methoxybenzyl hydroperoxide . 5 ) miscellaneous hydroperoxides • • si 3. Recrystallization 116 a. General ............... 116 b. Purification of hydroperoxides by re- crystallization .......... 116 1) 1,2,3,4-tetrahydro-l-naphthyl hydroperoxide ......... 116 2) 1,1-diphenylmethyl hydroperoxide 3) 1,2-diphenylethyl hydroperoxide . ill 4. Determination of purity 118 a. General ............... 118 b. Methods of estimating purity of hydro­ peroxides ............. 118 VI TABLE OF CONTENTS Page 1) titration •••••••••••••• 118 2) chromatography 119 3) melting point 121 4) refractive index •••••••••• 122 5) boiling point 122 E. Degradation of Hydroperoxides •«••••• 122 1* Acid catalyzed decomposition ............ 122 a. cinnamyl and a-phenylallyl hydroperoxides 122 b. a-ethylbenzyl hydroperoxide o • • • • • • 124 c. miscellaneous hydroperoxides . • • • o • 125 2. Base catalyzed decomposition ••••••• 125 a. benzyl hydroperoxide »••*••••*• 125 b* 1,2,3,4-tetrahydro-l-naphthyl hydro­ peroxide • 128 c. a-indanyl hydroperoxide ••»•••••• 129 d. miscellaneous hydroperoxides •••••• 129 3* Thermail decomposition ................ 130 a. a-methylbenzyl hydroperoxide • • • e • • 130 b. benzyl hydroperoxide •••••••••• 131 VI. SUMMARY..................................... 131 VII. BIBLIOG RAPHY................................. 134 AUTOBIOGRAPHY V I 1 INDEX TO TABLES Table Page I Comparison of Tolylcarbinols and Benzyl Alcohol with Methylphenylcarbinol » • • • • 25 II Reaction of Benzyl Alcohol........ .. 70 III Reaction of jri" and j^-Methylbenzyl Al­ cohols . 71 IV Reaction of Methylphenylcarbinol • o• • • • 73 V Reaction of a-Tetralol . « .............. 75 VI Reaction of a-Indanol •«•••• 76 VII Reaction of Benzhydrol ••••••••••• 78 VIII Reaction of p-Methoxy-a-methylbenzyl Alcohol «•••••••o •• 79 IX Reaction of Cinnamyl Alcohol o...... 81 IX-A Reaction of Miscellaneous Alcohols • • • • • 82 IX-AA Reaction of Miscellaneous Alcohols • • • • • 83 X Reaction of Propenylbenzene . 0 ..** 85 XI Reaction of d,4-Dimethylstyrene •»•••• 87 XII Reaction of a-Methylstyrene •••••••• 89 XIII Reaction of Indene ••••••• 92 XIV Purification of Hydroperoxides by Precipi­ tation as Sodium Salts......... o . 107 XV Purification of Hydroperoxides as Sodium Salts by Alkaline E x t r a c t i o n ............ « 116 XVI The Acid Catalyzed Decomposition of Hydro- 126- peroxides . ....................... 127 XVII The Base Catalyzed Decomposition of Hydro­ peroxides ........o... 130 XVIII Summary of Hydroperoxides Prepared • • o • • 133 viii I^^rRODUCTION The synthesis and characterization of hydroperoxides have increased in importance in recent years as the inter­ est in oxidation of hydrocarbons has spread. The produc­ tion of phenol and acetone by the air oxidation of cumene has been recently commercialized after a fifteen year period of study^, and other similar processes are possible. This general type of process offers a method of introduc­ ing a substituent on an aromatic ring without intermediate chlorination or sulfonation. As a result of the observa­ tion by members of the staff of API Research Project 4-5 at The Ohio State University that hydrocarbons react with oxy­ gen in the atmosphere (under normal storage conditions) to a greater or lesser degree depending on the type of hydro­ carbon, a program involving synthesis, purification and 2 properties of hydroperoxides was started. The occurrence of hydroperoxides as intermediates in the oxidation of hydrocarbons has been postulated and the circumstance of their formation has been tentatively ex­ plained by Walsh who postulated a free radical mechanism for their formation and decomposition.^ Numerous pure aromatic hydrocarbons have been prepared by API Research Project 4-5 and submitted to engine testing in the laboratories of General Motors Corporation.5 in view of the high qualities of such compounds as benzene and ethylbenzene and the rate of peroxide formation from ethyl benzene as compared with other aromatic hydrocarbons an investigation of the synthesis, purification and proper­ ties of aralkyl hydroperoxides was begun,A
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