REARRANGEMENTS QBSERVED DURING THE TRECHLOROMETHYLATION QF SOM£ POLYSUBSTITUTED BENZENES Thesis for the Degree of Ph. D. MICHIGAN STATE UNIVERSITY JERRY FREDERECK JANSSEN 1967 IffiRfiRY ‘ Michigan 3mm University T Highs: This is to certify that the thesis entitled REARRANGEMENTS OBSERVED DURING THE TRICHLOROMETHYLATION OF SOME POLYSUBSTITUTED BENZENES presented by Jerry Frederick Janssen has been accepted towards fulfillment of the requirements for Ph.D . Chemistry degree in /” await Med Major professor Date November 13, 1967 0-169 ABSTRACT REARRANGEMENTS OBSERVED DURING THE TRICHLOROMETHYLATION OF SOME POLYSUBSTITUTED BENZENES by Jerry Frederick Janssen The reaction of carbon tetrachloride with tetra- substituted benzenes in the presence of anhydrous aluminum chloride produces a mixture of polysubstituted benzotri— chlorides. The relative rates of reaction are in the order prehnitene>isodurene22-fluoro-l,3,5—trimethyl- “ benzene>2-chloro-l,3,S—trimethylbenzene>2—bromo—l,3,5— trimethylbenzene. The chief side product in the cases of isodurene and 2—fluoro-l,3,5—trimethylbenzene are the vicinally substituted products. That is, isodurene leads to chiefly 2,3,4,6—tetramethylbenzotrichloride and 2,3,4,5— tetramethylbenzotrichloride while 2—fluoro—l,3,5—trimethyl- benzene gives 3—fluoro—2,4,6—trimethylbenzotrichloride and M—fluoro—2,3,S—trimethylbenzotrichloride. The structures Of the rearranged products from the bromo- and chloro— compounds were not established but are assumed to be analogous to that derived from the fluoro-compound. Studies of the products derived from isodurene labeled with a trideuteriomethyl group in the 2 pos: rea rea sin prz *f Jerry Frederick Janssen position and again in the 5 position indicate that the reaction probably involves attack of the electrophilic reagent at various sites in the benzene ring followed by simple l,2—shifts of methyl groups to yield the observed product mixtureo The synthesis of twenty—four new polysubstituted benzene compounds is reporteda REARRANGEMENTS OBSERVED DURING THE TRICHLOROMETHYLATION OF SOME POLYSUBSTITUTED BENZENES By Jerry Frederick Janssen A THESIS Submitted to . Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1967 Vi cuseit 3—Wetg DEDICATION This thesis is dedicated to three teachers who have had a profound influence upon my teaching career: Mr° Loren Grout Roosevelt Junior High School Mason City, Iowa Dr. James We Kercheval University of Northern Iowa Cedar Falls, Iowa Dro Frederick Bo Dutton Michigan State University East Lansing, Michigan The decision to enter upon a career of science teaching is due in part to their encouragement, support and example. ii ACKNOWLEDGMENT The author wishes to express his sincere thanks to Dr° Harold Hart for his encouragement and support through- out the pursuit of this worko Appreciation is also ex— tended to the Chemistry Department of Michigan State University for financial support in the form of a teach- ing assistantship and to the E0 Io du Pont de Nemours Company for a du Pont Teaching Fellowship from September, 1965 to June, 19660 TEDICA ACTNOT LIST ( LIST ( INTRO REST SYNT TXPE TABLE OF CONTENTS DEDICATION ACKNOWLEDGMENTS o a o a o a o a a c . LIST OF TABLESG LIST OF FIGURES g a c a o c a . a o . INTRODUCTION 5 o o a . Io Introduction 9 c a o a II. The Jacobsen Reaction A. Scope 3 a a , o a a B. Mechanism III, The Trichloromethylation Reaction RESULTS AND DISCUSSION I . o a . a a SYNTHETIC SEQUENCES a a a c e o c a . . EXPERIMENTAL Io Trichloromethylation Reactions and Product Identification e O AD The Trichloromethylation of Mesitylene o o l: The Trichloromethylation of Mesitylene and Subsequent Methanolysis of the Producto 20 The Preparation of An Authentic Sample of Methyl 2, A ,6— Tri— methylbenzoate a a a, The Preparation of 2—Bromo— l,3,5—trimethylbenzene Page ii |_J (DUO DUI—1 l6 23 59 78 78 78 78 79 79 's.‘ " . _ "i4 B, b, The Preparation of 2,A,6— Trimethylbenzoic Acid . . ct The Preparation of Methyl 2,A,6—Trimethylbenzoate The Trichloromethylation of Isodurene l, The Preparation of Isodurene a. The Preparation of 2,A,6—Tri— methylbenzyl Chloride . b. The Preparation of Iosdurene. The Trichloromethylation of Iso- durene and Subsequent Methanoly— sis of the Product The Identification of Products Derived from the Trichloromethyl— ation of Isodurene and Methanoly— sis of the Product After Meth— anolysis, . . . a. The Preparation of an Authentic Sample of Methyl 2,3, A, 6— tetramethylbenzoate (l) The Preparation of A— bromo— l, 2, 3, 5— —tetra- methylbenzene . a (2) The Preparation of 2, 3, A, 6- tetramethylben— zoic Acid 5 (3) The Preparation of Methyl 2, 3, A, 6— Tetra— methylbenzoate . b, The Preparation of an Authentic Sample of Methyl 2, 3, 5, 6— Tetramethylbenzoate (l) The Preparation of 3— bromo— —l, 2, A,5— tetra- methylbenzene (2) The Prepara.tion of 2, 3, 5, 6— tetramethylben— zoic Acid (3) The Preparation of Methyl 2, 3, 5, 6—Tetramethy1ben— zoate Page 8O 81 81 81 81 82 83 85 85 85 86 87 88 88 88 89 CO 1. Page The Preparation of an Authentic Sample of Methyl 2 ,3 A ,5- -Tetramethylbenzoate. 90 (l) The Preparation of 2, 3, A— —Trimethylbenzyl Chloride , 9O (2) The Preparation of Pre— hnitene o . . 91 (3) The Preparation of 5— Bromo— l ,2 3, A— tetra- methylbenzene . o . . 92 (A) The Preparation of 2, 3, A ,5— —Tetramethylben— zoic Acid 5 a . 93 (5) The Preparation of Methyl 2 ,3 A ,5— Tetra— methylbenzoate. . o 93 The Preparation of an Authentic Sample of Methyl Pentamethylbenzoate , . 9A (1) The Preparation of 6— bromo—l,2,3,A,5—Penta— methylbenzene , a . . 9A (2) The Preparation of Pentamethylbenzoic Acid, 95 (3) The Preparation of Methyl Pentamethylben— zoate . . 96 Quantitative Studies of the Nuclear Magnetic Resonance Spectra of Mixtures of Methyl 2, 3, A ,6— —Tetramethylbenzoate and Methyl 2, 3, 5, 6— Tetramethylben— zoate , . 96 The Trichloromethylation of 2— Fluoro—l,3,5—trimethylbenzenee . . 97 The Preparation of 2-Fluoro— 1,3,5-trimethylbenzene, . a . 97 a. The Preparation of 2-Nitro- l,3,5—trimethylbenzene . . 97 b. The Preparation of 2,A,6— Trimethylaniline ; . . . 98 vi Page 0, The Preparation of 2— Fluoro— l 3, 5— Trimethyl— benzene , . a o . . 99 The Trichloromethylation of 2- Fluoro-l,3,5—trimethylbenzene and Subsequent Methanolysis of the Product 0 a . 99 The Identification of Products Derived from the Trichloromethyl— ation of 2—Fluoro-l,3,5—tri— methylbenzene and Subsequent Methanolysis of the Product, 0 o 100 a, The Preparation of an Authentic Sample of Methyl 3— Fluoro— 2, A, 6— trimethylbenzoate 101 (l) The Preparation of 2— bromo— A— fluoro— —l, L 5— —tri— methylbenzene , e 101 (2) The Preparation of 3— Fluoro— 2, A, 6— trimethyl— benzoic Acid 0 . 101 (3) The Preparation of Methyl 3— —Fluoro— —2, A, 6— trimethyl- benzoate , . 102 b, The Preparation of an Authentic Sample of Methyl A— Fluoro— 2, 3, 5— —trimethylbenzoate 103 (l) The Preparation of A— Bromo- -2— nitro— —l, 3— —dimethyl- benzene 103 (2) The Preparation of 3— Bromo— —L 6— dimethylaniline° 103 (3) The Preparation of A- Bromo— —2— fluoro— l, 3— —di— methylbenzene . 10A (A) The Preparation of 2, A— Dimethyl— 3— fluorobenzoic Acid . . 105 The Preparation of Methyl 2, A— Dimethyl— 3— fluoro— benzoate , 106 (6) The Preparation of 2, A— Dimethyl— 3— fluorobenzyl Alcohol 0 o 106 v (5 vii Page (7) The Preparation of 2,A- Dimethy1-3—f1uorobenzy1 Chloride . . . 107 (8) The Preparation of 3— F1uoro-,2,A-trimethy1— benzenel . . 108 (9) The Preparation of 6- Bromo- 3- fluoro— 1, 2, A- trimethylbenzene . . 108 (10) The Preparation of A- Fluoro— ,3 5- -trimethy1- benzoic 2Acid. . 109 (11) The Preparation of Methyl A- Fluoro- 2, 3, 5- -trimethy1- benzoate . . . . . . 110 The Trichloromethylation of 2- Chloro- l, 3, 5-trimethy1benzene . . 111 1. The Preparation of 2— Chloro- 1, 3, 5- -trimethy1benzene . . 111 2. The Trichloromethylation of 2- Chloro- 1, 3, 5-trimethy1benzene and Subsequent Methanolysis of the Product . . . 111 3. Identification of the Major Product Derived from the Tri- chloromethylation of 2— Chloro- l, 3, 5- -trimethy1benzene and Sub— sequent Methanolysis of the Product . . . . 113 a. The Preparation of An Authentic Sample of Methyl 3— Chloro— —2, A, 6— trimethyl- benzoate . a . . . . . 113 (1) The Preparation of 2— Bromo— —A— chloro— 1, L 5- trimethylbenzene . . 113 (2) The Preparation of 3— Chloro- ,A, 6— trimethyl— benzoic 2Acid. . 11A (3) The Preparation of Methyl 3— —Chloro- -2, A, 6— trimethyl— benzoate . . 11A viii Page E0 The Trichloromethylation of 2—Bromo— 1,3,5—trimethy1benzene. . . . . . 115 1. The Preparation of 2—Bromo—1,3,5— trimethylbenzene . o . . . . 2. The Trichloromethylation of 2- Bromo—l,3,5—trimethy1benzene and Subsequent Methanolysis of the Product . . . . a . . . 3. Identification of the Major Pro— duct Derived from the Trichloro- methylation of 2—Bromo—1,3,5— trimethylbenzene Followed by Methanolysis. . o o a . 115 115 a. The Preparation of an . Authentic Sample of Methyl 3- ., : Bromo—2,A,6-trimethy1benzoate. 117 : ‘- (1) The Preparation of 3— Bromo-2,A,6—trimethy1— benzoic Acid . a . . . 117 * (2) The Preparation of Methyl 3—Bromo-2,A,6—trimethy1— benzoate . o . . . 117 II. Mechanism Studies—-The Trichloromethy— lation of Deuterium Labeled Substrates. . 118 A. The Preparation of Model Compounds for the Assignment of Signals in the Nuclear Magnetic Resonance Spectra of Methyl Tetramethylbenzoates . . . . 118 1. The Preparation of an Authentic Sample of Methyl 3,A,5—trimethy1— benzoate . a . . . . . . . 118 a. The Preparation of A—Nitro— 1,2,3-trimethy1benzene . . . 118 b. The Preparation of 2,3,A—tri— methylaniline . a . . . 119 c. The Preparation of 6—Bromo— 2,3,A—trimethy1ani1ine a . . 119 do The Preparation of 5—Bromo— 1,2,3—trimethy1benzene . . . 120 e. The Preparation of 3,A,5— Trimethylbenzoic Acid . a . 121 ix f. The Preparation of Methyl 3,A,5—Trimethy1benzoate The Preparation of an Authentic Sample of Methyl 2,A,5—Tri— methylbenzoate . . . . a. The Preparation of 2,A,5— Trimethylbenzoic Acid. b. The Preparation of Methyl 2,A,5—Trimethy1benzoate The Preparation of an_Authentic Sample of Methyl 2,3,A-Tri— methylbenzoate . . . . a. The Preparation of A—Bromo— 1,2,3—trimethy1benzene b. The Preparation of 2,3,A— Trimethylbenzoic Acid. . c. The Preparation of Methyl 2,3,A-Trimethy1benzoate . B. The Trichloromethylation of 1,2,3,5— Tetramethylbenzene—Z',2{,2'-d3 . . l. The Preparation of 1,2,3,5- Tetramethylbenzene—2',2',2'—d3 a. The Preparation of 2,A,6— Trimethylbenzyl—a,a—d2 Alcohol . . . . . . b. The Preparation of 2,A,6— Trimethylbenzyl—c,d-d2 Chloride . . . . . . c. The Preparation of 1,2,3,5- Tetramethylbenzene— 2',2',2'—d, . . The Trichloromethylation of 1,2,3,5-Tetramethy1benzene— 2',2',2'—d3 and Subsequent Methanolysis of the Product C. The Trichloromethylation of 1,2,3,5- Tetramethylbenzene—S',5',5'—d3 . 1. The Preparation of 1,2,3,5— Tetramethylbenzene—S',5',5'-d3 X Page 122 123 123 123 12A 12A 125 126 127 127 128 128 129 129 129 III. Kit SUMMARY . LITERATURE APPENDIX, a. The Preparation of 3,A,5- Trimethylbenzyl-a, u—d2 Alcohol . . 129 b° The Preparation of 3, A ,5- Trimethylbenzy1——c, a— d2 Chloride . 130 c. The Preparation of 1, L 3, 5- Tetramethylbenzene— 5',5',5'-d3. . . . . . 131 2. The Trichloromethylation of 1,2,3,5—Tetramethy1benzene— 5',5',5'—d3 and Subsequent Methanolysis of the Product. . 132 III. Kinetic Studies-—The Relative Rates of Trichloromethylation of Five Tetrasub— stituted Esters . . . . . . . . 132 A. The Rate of Isomerization of Iso- durene in the Presence of Anhydrous Aluminum Chloride in Carbon Di- Sulfide at AO° . . 132 B. The Relative Rates of Trichloro— methylation of Five Tetrasubsti— tuted Benzenes at A0° . . 13A SUMMARY . . . . . . . . . . . 136 LITERATURE CITED . . o . . . . . 1A0 APPENDIX, SPECTRA. 1A7 xi ‘——r——i fl LIST OF TABLES Table Page I. Relative Rates of and Product Distribution from the Trichloromethylation of Five Polysubstituted Benzenes. . . . . . 26 II. The Rate of Isomerization of Isodurene in Carbon Disulfide . . . . . . . . 30 III. Relative Amounts of Two Products from the Trichloromethylation of Isodurene for Various Reaction Periods. . . . .- . 31 IV. Signal Assignments in the Nuclear Magnetic Resonance Spectra of Five Polysubsti— tuted Methyl Benzoates . . . . . . A1- V. Distribution of Products Obtained from the Trichloromethylation of Isodurene After Methanolysis. . . . . . a . . . 85 qure 1. Mass S ber met her Mei LIST OF FIGURES Figure 1. Mass Spectrum of Methyl 2,A,6—Trimethy1— benzoate Derived from the Trichloro— methylation of 1,2,3,5-Tetramethy1- benzene—2',2',2'—d3 and Subsequent Methanolysis. . . . . . . . . 2. Mass Spectrum of Methyl Pentamethyl- benzoate Derived from the Trichloro— methylation of 1,2,3,5—Tetramethy1— benzene-2',2',2'—d3 and Subsequent Methanolysis. . . . . . . . . 3. Mass Spectrum of Methyl 2,A,6—Trimethy1- benzoate Derived from the Trichloro- methylation of 1,2,3,5—Tetramethy1- bezene—5',5',5'—d3 and Subsequent Methanolysis. . . . . o , o o o A. Nuclear Magnetic Resonance Spectrum of Methyl 2,3,A,6—Tetramethy1benzoate De— rived from the Trichloromethylation of 1,2,3,5—Tetramethy1benzene—5',5',5'—d3 and Subsequent Methanolysis. . . . . A3 5. Mass Spectrum of Methyl 2,3,A,6—Tetra— methylbenzoate Derived from the Tri— chloromethylation of 1,2,3,5—Tetra— methylbenzene—5',5',5'—d3 and Subsequent Methanolysis. . . . .- . . . . . AA 6. Nuclear Magnetic Resonance Spectrum of Methyl 2,3,A,6—Tetramethy1benzoate De— rived from the Trichloromethylation of 1,2,3,5—Tetramethy1benzene—2',2',2'-d3 and Subsequent Methanolysis. . . . . A5 7. Mass Spectrum of Methyl 2,3,A,6—Tetra- methylbenzoate Derived from the Tri— chloromethylation of 1,2,3,5—Tetra— methylbenzene—2',2',2'-d3 and Subse— quent Methanolysis. A7 xiii 11. Mass 1 m C II c i I I i i i i I i i Figure 8. Nuclear Magnetic Resonance Spectrum of Methyl 2,3,A,5—Tetramethylbenzoate De- rived from the Trichloromethylation of 1,2,3,5—Tetramethy1benzene—5',5',5'—d3 and Subsequent Methanolysis. . o a u ' \O . Mass Spectrum of Methyl 2,3,A,5—Tetra- methylbenzoate Derived from the Tri— chloromethylation of 1,2,3,5—Tetra— methylbenzene-5',5',5'—d3 and Subse— quent Methanolysis. . . . . o . . 10. Nuclear Magnetic Resonance Spectrum of Methyl 2,3,A,5-Tetramethy1benzoate De- rived from the Trichloromethylation of 1,2,3,5-Tetramethylbenzene-2',2',2'-d3 and Subsequent Methanolysis. . . . . 11. Mass Spectrum of Methyl 2,3,A,5—Tetra— methylbenzoate Derived from the Tri- chloromethylation of 1,2,3,5-Tetra— methylbenzene-2',2',2'-d3 and Subse- quent Methanolysis. . . . 0 O 0 ° In aromatic of subs1 frequen‘ this ph Several substit have re ch10ri< duce t] CH .1 3 Carli of t}. INTRODUCTION 1. Introduction In the substitution of already highly-substituted aromatic compounds with bulky electrophiles, migration of substituents to previously unoccupied positions has frequently been observed. The most notable example of this phenomenon is the widely studied Jacobsen reaction. Several examples of similar anomalous electrophilic substitutions have been reported. Rekker and Nauta (l) have reported the reaction of durene with the acid chloride of 2,3,5,6-tetramethy1benzoic acid (I) to pro- duce the rearranged ketone (II). CH 0 c1 3 \\ I CH3 C CH3 CH CH 0 CH3 CH3 3 3 AlCl3 CH3 C4 CH3 CH3 H3 CH3 CH3 CH3 CH3 (1) (II) Carlin and Moores (2) have observed that the reaction of the mesithylhydrazone of cyclohexanone (III) in boiling gll tetrahydrocar‘ (III The following molecular mi; CH 3 CH; CH. t CH; CH3 CH2(C “though tho tute cases been no 3111 ties to it. migration C in boiling glacial acetic acid leads to the unexpected tetrahydrocarbazole (IV). CH3 CH3 CH 3COOH NH_N':'C> Reflux CH3 (III) (IV) The following ring closure reactions also involve intra- molecular migrations of substituent groups: CH3 CH PPA CH2 (CH2 )2 COOCH (3) CH3 CH3 0 Anhydrous (A) 0 CH2(CH2)ZCOOH Although the above examples do not technically consti— tute cases of the Jacobsen reaction because there has been no sulfonation, they bear many striking similari- ties to it. All of the cases exhibit intramolecular migration of substituents to vicinally substituted i t products in l similarities that the ham all such rea ties and dif the rearrang reactions wt torioal tree first part c The r DOunds upon after Oscar A1 exceller 19112 may be (6), Subs of the Jae alkyl grou Centrated the“ be he temptil‘atux treatment acids der: Ention Q products in the presence of an acid catalyst. These similarities have prompted one author (5) to suggest that the name "Jacobsen reaction" be broadened to cover all such reactions. In order to point up the similari— ties and differences between the Jacobsen reaction and the rearrangements observed during the trichloromethylation reactions which occupy the present study, a brief his— torical treatment of these two reactions will occupy the first part of this thesis. II. The Jacobsen Reaction 9 A. Scope The rearrangement of polysubstituted aromatic com- pounds upon sulfonation is termed the Jacobsen reaction after Oscar Jacobsen, its principal early investigator. An excellent review of the published literature prior to 19A2 may be found in the first volume of Organic Reactions (6). Substituents known to migrate under the conditions of the Jacobsen reaction are iodine, bromine, chlorine and alkyl groups. Normally the substrate is mixed with con— centrated sulfuric acid or fuming sulfuric acid and may then be heated briefly or allowed to stand at room temperature for extended periods. The product of this treatment is a mixture of substituted benzenesulfonic acids derived from both intra- and intermolecular mi— gration of the substituents. The most common products of intramole< tuted molecui desulfonated synthetic ap valuable vic Thus prehnit isodurene ar from the re: cumenes. By-pr dioxide and The ease wi nature and line. If . occur even and bromob duce first then 1,231 bellzehe (' tent in t‘ not react \N W the Dolyn made to 1 hemimell: and Web Wins W111 he of intramolecular rearrangements are vicinally substi— tuted molecules. Since the sulfonic acids are easily desulfonated by steam distillation, the reaction has synthetic application in the production of the more valuable vicinal products from the more common isomers. Thus prehnitene* can be produced from durene and/or isodurene and the more valuable 3-halo—pseudocumenes from the readily available 5-bromo— and 5-chloropseudo— cumenes. By-products of the Jacobsen reaction are sulfur dioxide and (often) tarry masses and polymeric materials. The ease with which rearrangement occurs depends upon the nature and number of substituents attached to the benzene ring. If only halogen is present, rearrangement will occur even if the ring is monosubstituted. Thus iodo- and bromobenzene will react in stepwise fashion to pro- duce first p-dihalobenzene, next 1,3,5-trihalobenzene, then 1,2,A,5-tetrahalobenzene, and finally hexahalo- benzene (7). The reaction conditions must be more strin— gent in the case of bromobenzene, and chlorobenzene does not react in this manner. *To facilitate the discussion, the common names of the polymethylbenzenes will be used when reference is made to the parent hydrocarbons; i.e., mesitylene (1,3,5- trimethylbenzene), pseudccumene (1,2,A—trimethy1benzene), hemimellitene(1,2,3-trimethy1benzene), isodurene (1,2,3,5— tetramethylbenzene), durene (1,2,A,5-tetramethy1benzene), and prehnitene (1,2,3,A-tetramethy1benzene). When re- ferring to derivatives of these hydrocarbons, recourse will be made to the IUPAC naming rules to avoid ambiguity. A study that increasi‘ the migration sults in the product. The gems in these l>Br>Cl. F01 sulfonate um whereas the 1 high yield. already been With U “WI occur ducts result Lindel‘so disy fall into a: intramolew C0"mounds h rSection (g has been m In tl reactiOn 1: containing alkyl Side hemimelnt mcrely Sul A study of the polyalkylhalobenzenes (8) has shown that increasing the number of alkyl substituents favors the migration of the halogen atom but simultaneously re- sults in the production of greater amounts of tarry by— product. The relative migratory aptitude of the halo— gens in these compounds seems to be in the order I>Br>C1. For example, the monochloroxylenes merely sulfonate under conditions of the Jacobsen reaction A, whereas the monoiodoxylenes afford polyiodoxylenes in high yield. The reaction of the halopseudocumenes has , Vin: already been cited. With monochlorotetramethylbenzenes, migration of ‘ »A methyl occurs with the expected vicinally substituted pro- ducts resulting. The iodotetramethylbenzenes tend to undergo disproportionation whereas the bromo—compounds ‘ / fall into an intermediate class showing both inter- and intramolecular migration products. Only a few fluoro- compounds have been studied in connection with the Jacobsen reaction (9). No instance of migration of a fluorine atom has been noted. In the case of the polyalkylbenzenes, the Jacobsen reaction is limited to tetra- or pentasubstituted benzenes containing tetramethylene rings and/or short, unbranched alkyl side chains. Mesitylene (10), pseudocumene (10), hemimellitene (11), 1,3,5- and 1,2,A-triethy1benzene (l2) merely sulfonate without rearrangement. Tetraalkylbenzenes fi in which thr eliminate a sulfonic ac Dure produce pr greater in and 1,2,3, her (12) t acid. Pr rent (10) arrange ( ethyl or ture whic dispropo prehniten The saturate< limited ‘ rings . by Schrc phenantl in which the substituents are isopropyl or larger tend to eliminate alkyl groups resulting in trialkylbenzene- sulfonic acids (13). Durene (10, 1A) and isodurene (10, 15) react to produce prehnitenesulfonic acid although the yield is greater in the case of durene. 1,2,A,5-tetraethy1benzene and 1,2,3,5-tetraethy1benzene react in an analogous man— ner (12) to produce 1,2,3,Antetraethylbenzenesulfonic acid. Prehnitene is only sulfonated without rearrange- ment (10). The ethyltrimethylbenzenes similarly re- arrange (13, 16, 17) but migration of either methyl or ethyl or loss of either results in a complex product mix— ture which is difficult to analyze. Pentamethylbenzene disproportionates (18, 19) to give hexamethylbenzene and prehnitenesulfonic acid. The Jacobsen reaction with compounds containing saturated rings fused to the benzene nucleus seemsto be limited to those substances containing tetramethylene rings. Octahydroanthraceneu9~su1fonic acid (V) was shown by Schroeter and thzsky (20) to rearrange to octahydro- phenanthrene-9—su1fonic acid (VI) SO3H (V) fi in good yie studied by varied wit] paralleled tetralins substitue peoted vi When one group we: not uncle: , group, 1; methylen the n-pr Branchec‘ Suiting s reactio did not in good yield. A series of dialkyltetralins were studied by Smith and Lo (21) and although the results varied with the nature of the substituents, the results paralleled those of the tetraalkylbenzenes to which the tetralins were structurally related. When both alkyl R' R R stoq ' ———-—————e» R. (VII) (VIII) (a) R = R' = CH3 (b) R = R' = 02H5 (C) R = CH3, R' = I’l—CgH'; (VIId) R = CH3, R' = iso—C3H7 (VIIId) R = CH3, R' = H substituents were methyl (VIIa) or ethyl (VIIb) the ex- pected vicinal products (Villa) and (VIIIb) were obtained. When one of the groups was n-propyl (VIIc) the larger group was found in the 5=position (VIIIc). Since it had not undergone rearrangement to the more stable isopropyl group, the workers concluded that it was the tetra- methylene ring which had opened and reclosed ortho to the n-propyl group rather than the latter migrating. Branched groups such as isopropyl (VIId) were lost re- sulting in monoalkyltetralins (VIIId). s—Hydrindacene (IX) did not undergo the Jacobsen reaction (22) and 5,6,7,thetrahydrobenszjindan (X) did not rearrange but was dehydrogenated by the action <1) (IX) of the sul The mechanist has been not the p Thus, Smi acid will with phos are unaff servatior bill on ‘ phosphor of the s 0~xylene nation. A: mechani disuli‘o mechani 4? GOO GOO GOO (IX) (X) (XI) of the sulfuric acid to (XI). B. Mechanism The Jacobsen reaction has been the subject of much . 1“ mechanistic speculation (see for example 23, 2A). It Ar.f has been shown that it is probably the sulfonic acid and , Ittg" not the parent hydrocarbon which undergoes rearrangement. A .‘Ih'd Thus, Smith and Cass (10) have shown that durenesulfonic acid will rearrange to prehnitenesulfonic acid in contact with phosphorus pentoxide whereas the parent hydrocarbons are unaffected by this treatment. Support for this ob- servation is found in the recent work of Marvell and Gray- bill on the rearrangement of durenesulfonic acid in poly- phosphoric acid (25). They found that when in PPA all of the sulfonating agents were removed by scavenging with o-xylene, the only reaction which occurred was desulfo- nation. Arnold and Barnes (22) have proposed an ionic mechanism involving the formation of an intermediate disulfonic acid. Applied to the case of durene, the mechanism is as follows: (a) t AA rn SET (a) the hydrocarbon is sulfonated H SO3H 303H 3H3 H3 CH3 CH3 CH CH3 ‘— ‘— H H 3 3 CH CH 3 3 3 CH3 CH3 (XII) (b) because the sulfonic group in (XII) is sterically crowded, contributions to the ' '5 resonance hybrid by canonical structures such as (XIIa) are diminished. OH o—s—o' CH3 CH3 CH3 CH3 (XIIa) The resulting diminished positive charge in the ring permits a second sulfonation which takes place preferentially at a position meta to the first sulfonic group. SO3H SO3H SOgH CH3 CH3 CH3 CH3 CH3 CH3 ._.___. . .1.... —'—$' w CH3 CH3 CH3 H3 CH3 SOgH soy m, The abov ' ward by PPOPlil'T propyl-E furic a: but othl Barnes rearran refutat work of tetrae' of the than 9 0n thi hydrop and e1 shift 10 (c) attack of the displaced alkyl cation at the position of the most hindered sulfonic acid group results in the observed rearranged product. SO3H CH3 SOaH CH3 ' (3 CH CH3 + CH CH3 CH3 —so3H@ CH CH3 —_2. —__9. ,. CH3 SO3H CH3 SO3H CH3 $03H ‘ :j The above mechanism is subject to the criticism put for- ward by Smith and Lo (21). They have showed that 6-n- propy1-7-methy1tetralin (VIIc) was converted to 5-h- propy1-6—methy1tetralin (VIIIc) by the action of sul- furic acid. If the migration had involved a solvated but otherwise unencumbered alkyl cation as Arnold and Barnes suggest, one would expect the n—propyl cation to rearrange to the more stable isopropyl cation. Further refutation of the above mechanism is provided by the work of Marvell and Webb (26). They found that 1,2,A,5- tetraethylbenzene labeled with C“+ at the alpha position 0f the ethyl groups underwent rearrangement with better than 90% retention of labeling at the alpha position. On this basis they ruled out any process involving hydrogen-bridged structures, equilibria between ethylene and ethyl cations, or equilibria involving hydride shifts in ethyl carbonium ions. Furthermore, the migrating all the aromatic that the J ac 1,2,A,5-tetr prehnitene a crossing. The at accommodate migrating g ring. Such been propos sulfonatior tions in d1 CH l 3 The ion (: Shii‘ts in mediates Until the is formec' (X1119) . 11 migrating alkyl group cannot become completely free of the aromatic ring since Goto and Suzuki (13) have shown that the Jacobsen reaction with a mixture of durene and 1,2,A,5-tetraethylbenzene results predominantly in prehnitene and 1,2,3,A—tetraethylbenzene with little crossing. The above mechanism of Arnold and Barnes can be accommodated to these criticisms if one assumes that the migrating group is never completely free of the aromatic ring. Such a mechanism for the Jacobsen reaction has been proposed by Dewar (27). He suggests that the initial sulfonation step occurs at one of the substituted posi- tions in durene resulting in the benzenonium ion (XIII). so3H CH CH CH3 3 3 _ CH ‘—-'-'——’ 3 (XIII) The ion (XIII) then rearranges via a series of 1,2- shifts involving alternately sigma—complexed inter- mediates (XIIIa) and pi—Complexed intermediates (XIIIb) until the thermodynamically most stable product (XIV) is formed by the deprotonation of its conjugate acid (XIIIC). Diapr and p tack such sita' Kilp V01v and tube d0m: anhj hvo 12 SOaH SO3H CH5 CH3 CH3 H3 ___—4» CH 3 CH3 CH3 CH3 (XIII) (XIIIa) \\\\ CH3+ T SO3H / C: > CH3 803H SO3H CH I %:;M M: (XIIIb) CH3 (XIV) (XIIIc) Disproportionation products such as the trimethylbenzene- and pentamethylbenzenesulfonic acids arise from 3N2 at— tack of an unsubstituted molecule upon a sigma complex such as (XIIIa or XIIIc). In opposition to the above mechanisms which neces- sitate sulfonation and rearrangement of the sulfonic acid, Kilpatrick and Meyer (28) propose a mechanism which in— volves desulfonation, rearrangement of the hydrocarbon and irreversible sulfonation of the vicinally substi— tuted benzene. Although durene and prehnitene give pre— dominantly the more basic isodurene in mixtures of anhydrous HF and boron trifluoride (29), any of these Hydrocarbons sulfonates to give almost exclusively M. “ prehnitene These worl nation, r1 prehniten an accumu in chart DS. rn rn rn mH’UUHPUU For thi “fiction km in the otl cast .1 and R1 exchan legs 5 (iv), l3 prehnitenesulfonic acid in concentrated sulfuric acid. These workers thus conclude that sulfonation, desulfo— nation, rearrangement and resulfonation to the stable prehnitenesulfonic acid provide a cycle which leads to an accumulation of the latter. This scheme is presented in chart form below: _;=a;s ISA k1 k2 I _% DSA ___.. s + I)<{/’1L k. d‘——— k k 'H -1 k_3 P “:2“; PSA : H [‘3‘ BSA = durenesulfonic acid PSA = prehnitenesulfonic acid ISA = isodurenesulfonic acid D = durene P = prehnitene I = isodurene S = SOSH+ For this mechanism to explain the observed facts in con- nection with the Jacobsen reaction it is necessary that k_6 in the above equilibrium be small in comparison with the other rate constants. However, serious doubt is cast upon this mechanism by the observation of Bohlmann and Riemann (30) that prehnitenesulfonic acid rapidly exchanges sulfur with S35 labeled sulfuric acid. Un- less such exchange involves a symmetrical ion such as (XV), it is doubtful that the Kilpatrick mechanism can compl action of Ba: reaction peered u action m mechanis Their me hhnn sDecies- Species ation 0 durene The bf diQXil 44444T____________-!gg!'. 1L1 CH3 SO3H 4 803H CH3 (xv) can completely explain the course of the Jacobsen re— action of durene. Based upon their observation that the Jacobsen reaction exhibited an induction period which disap— peared upon the addition of peroxydisulfate to the re- i, [‘Trf action mixture, Bohlmann and Riemann suggest that the ‘ ”WM: mechanism proceeds rather by a radical—cation mechanism. Their mechanistic proposal closely parallels that of Kilpatrick in that they suggest that it is a desulfonated SpecieSthat rearranges. They suggest, however, that this speciesis a radical cation (XVI) formed by the dissoci— ation of the hindered durenesulfonic acid rather than durene itself. SOgH H H3 CH3 CH3 . CH3 +H+ CH3 CH3 H3 CH3 CH3 CH3 CH3 CH3 (XVI) The bisulfite radical can dissociate to give sulfur dioxide and a hydroxyl radical. Equilii durene nation sulfor pref DPO< two Suf Uni 15 '5‘- ~803H + SO2 + -OH Equilibration of the radical cations of durene, iso- durene and prehnitene followed by reversible sulfo— nation leads to an accumulation of the stable prehnitene- sulfonic acid. Although this mechanism satisfactorily accounts for the by—product sulfur dioxide it suffers from the same criticisms of the Kilpatrick mechanism. Bohlmann and Riemann showed that when the starting durene had been ring-labeled with CH at the four methylated positions, the two unmethylated positions in the re- sulting prehnitene were not equally labeled. The posi- tion bearing the sulfonic acid group in the product con- tained 17.3% of the original CH whereas the adjacent unsubstituted position contained only 13.0%. If this prehnitenesulfonic acid had been formed from prehnitene produced by equilibration of the hydrocarbons, these two positions should have been equally labeled. It would appear that to date there has not been sufficient experimental data presented to define a unique mechanism for the Jacobsen reactiono Indeed, it is possible that for many of the reactions classified under the fiffers f1 ukylbenz< ment that nation of by a seri The majox most stat that of ‘ A organic the met} itharasc} Tadical on capb Olefins to a V5 SUCCESS the act (33% °arbin the th the DI n3“ 16 under the heading "Jacobsen reaction" the mechanism differs from that involved in the sulfonation of poly— alkylbenzenes. However, there seems to be common agree- ment that the rearrangement probably involves proto- nation of the initially formed sulfonic acid followed by a series of reversible l,2-shifts and deprotonationa The major product observed at equilibrium is then the most stable sulfonic acid which may not necessarily be that of the most stable polysubstituted substrate isomer, III° The Trichloromethylation ReactiOn A trichloromethyl group may be introduced into an organic molecule by any one of three means depending upon the method by which the ~CCl3 moiety is generated. ‘ Kharasch (31) demonstrated in 1945 that trichloromethyl radicals could be generated by the action of peroxide on carbon tetrachloride or chloroform and would add to olefinso Since that time the reaction has been applied to a variety of halomethanes and olefinic substrates with success (32)o The trichloromethyl anion, generated by the action of bases upon chloroform adds to aldehydes (33-36) and ketones (37-40) to produce trichloromethyl— carbinols° More recently (Ml) it has been shown that the thermal decomposition of sodium trichloroacetate in the presence of anhydrides leads to trichloromethyl keto-acids or trichloromethyllactolsa duce a howeve -CC13 is ne< subst anhyd speci mati< 17 None of the preceding reactions serves to intro- duce a trichloromethyl group into an aromatic nucleus, however. The generation of a trichloromethyl cation or -CCl3 group in which the carbon is electron deficient is necessary for the trichloromethylation of aromatic substrates. The reaction of carbon tetrachloride with anhydrous aluminum chloride appears to provide such a speciesCzigg_infra). The initial studies of the reaction between aro- matic hydrocarbons and carbon tetrachloride comprise a part of the work performed by Charles Friedel and James Mason Crafts (42—44) on the general reaction which now bears their names. By adding anhydrous aluminum chloride to a flask containing carbon tetrachloride and benzene in a 1:20 molar ratio they were able to produce a mixture of tri- and tetraphenylmethane in which the latter compound predominated, Boeseken (45) reasoned that the reaction proceeded by a stepwise mechanism in which the chlorine atoms were successively replaced by hydrocarbon groups. Norris and Green (#6), employing the technique of Friedel and Crafts, had earlier shown that chloro— and bromo— benzene gave the ccrresponding substituted benzophenone dichlorides° Thus, it seemed possible to Boeseken to arrest the reaction at the first step to produce benzo- trichlorides by adding one of these substrates to an excess of carbon tetrachloride. Using this method he was able to cite ev chloro- did n01 them ti in a m then h adih chlori dichl the h dence chlor main1 Boes dich mate whic Wher and met Der met l8 :ite evidence of having produced small amounts of p- :hloro+ and p-bromobenzotrichloride (45). Although he lid not isolate the compounds themselves, he converted ;hem to the corresponding benzoic acids by hydrolysis .n a mixture of glacial acetic and sulfuric acids. Jhen he attempted to prepare benzotrichloride by adding l dilute solution of benzene to excess carbon tetra— :hloride, he succeeded in isolating only benzophenone lichloride in 80~90% yield. A careful examination of :he hydrolyzate from this reaction failed to produce evi- lence of any benzoic acid (and therefore any benzotri— :hloride). Employing this method, in which care is taken to laintain the carbon tetrachloride always in excess, Boeseken converted toluene to p,p'-dimethylbenzophenone lichloride in good yield. m-Xylene gave some resinous material and he was unable to isolate the dichloride vhich decomposed with the evolution of hydrogen chloride hhen he attempted its distillation. In an extension of this work, Rolih and Peters (U7) nd again Hart and Fish (48) were able to produce penta— ethylbenzotrichloride by the trichloromethylation of entamethylbenzene. Hart and Fish later employed this eaction with success in the preparation of 2,4,6—tri— ethylbenzotrichloride from mesitylene (H9)° However, when t1 duct w; tetram Simil; react norma addit hete: the a SuSpe exce: immet Suma‘ aren the main nati c01c 19 n they attempted the reaction with durene, the pro- t was the unexpected rearranged compound 2,3,M,5- ramethylbenzotrichloride (XVII). CH3 CH3 AlC13 CCIH: HO CH3 CH3 0013 CH CH3 I CH3 CH3 (XVII) lilarly isodurene rearranged during the course of the .ction to produce (XVII) while prehnitene reacted in a -mal fashion, also to produce (XVII). Two notable features of the preceding reaction, in lition to the rearrangements noted, are its color and (erogeneity. In normal practice a dilute solution of . aromatic substrate is slowly added to a stirred .pension of anhydrous aluminum chloride in a large :ess of carbon tetrachloride. The solution almost lediately develops a red—orange color which is pre- lably due to the formation of a complex between the ‘ne and aluminum chloride. As the reaction proceeds ‘ color changes to a deep purple, the color which re- ns until the aluminum chloride is hydrolyzed. Exami- ;ion of the flask contents shows, however, that the tor resides almost exclusively in the lower semi-solid phase flask chlori that t alumix the h; the f carbo produ Lewis T8081 2O Lase which has been spread over the walls of the reaction .ask by the stirring action; the upper carbon tetra— Lloride solution is almost colorless. This suggests Lat the reaction product is probably complexed with the .uminum chloride in some form and is released only in 1e hydrolysis step. This conjecture is borne out by xe fact that hydrolysis and examination of the upper Lrbon tetrachloride phase yields no detectable reaction ‘oduct. That aromatic compounds will complex with strong awis acids has been known since 1875 (5Q 51). More acent investigations have shown that a proton co—acid s needed as well (52, 53). Since no precautions are ‘ t , ‘ tken to dry the aluminum chloride prior to its use in 1is reaction, there are undoubtedly traces of water pre- ant in the reaction mixture. The necessary co-acid (HCl) 9 therefore present and it is probable that as the romatic material is added to the flask it becomes immedi— 1ely complexed with the aluminum chloride. Brown sug— sts (53) that the arene, aluminum chloride, and the oton co-acid are complexed in a l:l:l molar ratio in e form of a benzenonium ion salt of the hypothetical id HAlXu. This reaction is typified by the behavior toluene shown below: The e chlor (hrH) some furit as H 21 CH3 H CH3 ___—> — AlXu complex is capable of dissolving additional aluminum aride through the formation of complexes of the type i)+(AlnX3n+l)—. This behavior is not dissimilar in a respects to the behavior of sulfur dioxide in sul- ic acid to produce the higher oxy—sulfur acids such H28207’ stsolo’ etc. Evidence has also been presented that carbon tetra- oride will weakly interact with aluminum chloride. lace and Willard (54) have shown that carbon tetra— oride will rapidly exchange its chlorine with solid minum chloride even at the freezing point of the former. ce no reaction at all occurred when the aluminum oride was dissolved or when both it and the carbon rachloride were in the vapor phase, it is evident t an aluminum chloride surface is necessary. The for- ion of carbonium ions of the type 0013+ was ruled out the basis of bond energy calculations. The authors or a mechanism in which an induced dipolar carbon rachloride molecule is adsorbed on the surface of the .minum chloride lattice at a charge site. Desorption then accompanied by exchange. it been alumz‘ chlo‘ stro nece star sol: pha chl 22 Benzene and carbon tetrachloride vapors have also n shown to undergo a Friedel-Crafts reaction with minum chloride, but again only when an aluminum oride surface is present (55). These findings 'oneg suggest that an excess of aluminum chloride is essary for the trichloromethylation of aromatic sub— .nces in order to assure that there is always some .id undissolved aluminum chloride present in the lower Lse of the reacting mixture. The excess carbon tetra- .oride not only serves as a diluent for the hydrocarbon prevent formation of polynuclear products, but also >bably tends to shift the equilibrium controlling the Junt of carbon tetrachloride adsorbed on the aluminum Loride surface. excel with form RESULTS AND DISCUSSION The trichloromethylation of mesitylene afforded an allent yield of 2,4,6-trimethylbenzotrichloride (XVIII) 1 no detectable amounts of rearranged isomers being led. 0013 CH3 A1013 CH3 CH3 _—9 COIL+ CH3 CH3 (XVIII) ever, reaction of isodurene with carbon tetra— )ride in the presence of anhydrous aluminum chloride 40° produced a mixture of five polymethylbenzotri— >rides in which 2,3,4,6—tetramethylbenzotrichloride C) and 2,3,4,S—tetramethylbenzotrichloride (XX) lominated. 23 n? l 81ml prod ahm err: my] 24 [—> (XVIII) CH3 CH3 --i> (XIX) 0013 Q CH3 CH3 0013 ——> (XX) CH3 CH3 CCI3 CH3 CH3 # CH3 CH3 Llarly 2—fluoro—l,3.5-trimethylbenzene reacted to luce a rearranged product corresponding to (XX) re, but the reaction appears to be free of other re— lngement products in this case. That is, tri— >romethylation of 2—fluoro—l,3,5—trimetylbenzene at afforded 3—fluoro-2,4,6-trimethylbenzotrichloride 3) and 4—fluoro—2,3,S-trimethylbenzotrichloride II) but no detectable isomers. CH [ CH3 A1013 CH3 0013 h 25 F F F —-u——’- 001, + 0130H3 CH3 CH3 0013 (XXI) (XXII) 2-Chloro-, and 2-bromo-l,3,5-trimethylbenzene undergo trichloromethylation less readily than the above sub- strates and the amount of rearranged isomer produced in each case (assumed to correspond to (XXII above) was correspondingly reduced. Although the rearranged isomer derived from the trichloromethylation of 2—fluoro-l,3,5-trimethy1benzene, followed by methanolysis was conclusively shown to be methyl 4-f1uoro-2,3,5-trimethy1benzoate by an unambigous structure proof, the structures of the rearranged pro— ducts derived from 2-chloro- and 2—bromo—l,3,5-trimethyl- benzene were not determined. These results are summarized in Table I. Because of the difficulties encountered in obtaining precise kinetic data for Friedel-Crafts reactions, the relative reactivity rates listed in Table I are only approximate. Batch work-up procedures were employed and there was [ difficulty in strictly reproducing reaction conditions ‘ from one experiment to another. l l .mmoooo I w .udmsoflomndm wears; .uoozeoou ncpmm Hapou ”Etched mm ocmmmooxmo .ccmhsvomfl on $3..» "NU mammm i: ems em 8. + 3.0 LAW cm “NH sew Ho mo. H em.o \HHHHE/ Ho mom RS. m To H 04 \Q _ m no “OOH mmo H. H a.m - mMHHH me . Rh “mm mm see em meo. oo.H \HHWHF/ s _/ _/ e _/ mm s A“ \x x eonsmflsemeOhoneouce mseupmesm x x x w peessusmesm co amuse e>HpeHem e.eeonp:efieemfim poseoem mmzmwzmm QmBDBHEmmmeqom m>Hm mo ZOHBisodurenea2— luoro—,>2-chloro-,>2—bromo—l,3,5—trimethylbenzene, is learly established. It is also clear that the amount f rearranged product in each case corresponding to ethyl 2,3,4,5—tetramethylbenzoate parallels the re— ctivity order. The trichloromethyl compounds produced in this tudy are difficult to work with for two reasons. First5 he compounds hydrolyze in moist air to the correspond- ‘ng benzoic acids. Second, methods of purifying indi- idual members of the series or of separating mixtures of them meet with particular problems. The corrosive nature of the compounds precludes their separation on gas—liquid chromatographic columns or on elution columns of acidic or basic adsorbents. The tendency of some members of the series to lose hydrogen chloride when heated (56) prohibits their distillation. For these reasons the benzotrichlorides obtained in various experi— ments in this study were converted to their corresponding methyl benzoates by solvolysis in boiling methanol. This facilitated their separation by glc methods and their identification by comparison to known or easily prepared compounds. Examination of the data presented in Table I indi— cates that in addition to the expected product the impor— tant minor product in each case is the vicinally sub atl 28 ubstituted molecule. In this regard, the trichloromethyl— tion reaction of these substrates closely parallels the acobsen reaction. There are three mechanistic possibilities leading o the formation of the rearranged vicinally substituted roduct: (l) the substrate could be rearranged by the ction of aluminum chloride followed by trichloromethyl- tion of the resulting mixture of hydrocarbons; (2) the substrate could be trichloromethylated and the product ‘ I (f isomerized to the vicinally substituted isomer by the ; “the aluminum chloride; or (3) a series of competing reactions dnvolving attack of the ~CCl3 moiety at various positions On the benzene ring and involving, in certain cases, 1,2— alkyl shifts leads to the product mixture observed. In view of the fact that anhydrous aluminum chloride is known to isomerize polysubstituted aromatic compounds (57*59) the first mechanistic possibility appears at first quite reasonable. Indeed, in a simple experiment in which isodurene was shaken at 40° with aluminum chloride, a mixture of hydrocarbons was produced in which there was 1.4% prehnitene. However, although these iso- merizations in the trichloromethylation reaction mixture are undoubtedly competing with the main reaction (i.e., the reaction of the hydrocarbon with carbon tetrachloride) the first mechanism cannot entirely account for the relatively large amount of rearranged material arising 29 from the trichloromethylation of (at least) isodurene. When isodurene was stirred with anhydrous aluminum ‘chloride in carbon disulfide at the same "concen- ‘probable that the rate of isomerization of isodurene to , tration"* as in the trichloromethylations of isodurene, no prehnitene was detected in the resulting hydrocarbon until 1 1/4 hours had elapsed (cf. Table II). Yet in one experiment in which a trichloromethylation reaction of isodurene was quenched after only six mintues of re— 42 action time the product mixture contained 23% of tri— chloromethylprehnitene (isolated as methyl 2,3,4,5- tetramethylbenzoate). It is possible but highly im— prehnitene is sufficiently faster in carbon tetrachloride than in carbon disulfide to account for the observed re- sults. The second proposal cannot be entirely eliminated as the mechanistic course of the reaction, but the data presented in Table III speak strongly against it. When isodurene was trichloromethylated under varying reaction times, the ratio of trichloromethylisodurene to tri- chloromethylprehnitene remained substantially constant. Unless the equilibrium between these two materials was *The hydrocarbon reacts with the aluminum chloride to produce a lower semi-solid phase. Most of the sub- strate is present in this phase in equilibrium with a Small amount in the upper solvent phase. .ccohsv one oCcQSpomfl mpmzmdom pod UH: oz com: :E5H00 cam ones ems .24.. was $5 $6 rim am; am; seem a: is; “9.. was $5 24 mm; :3 2 $5 -l ea its a; $5 om; em; 8 {I in $2 1!. I- In: 34 em; em. 0 I: III Rog .ia n». Ii mmé emé om so :1: VIII Rooa II: III Ill mH.H em.H OH WIIIIKKIIIJ - l _\ COQLMoogoh: AzHHmeHCHV Amouscazv Uohw>oomm mo mamas . mcohdcomH mo mEmLo mafia coauommm moonsm00hcmm ochc>ooom mo coaufionEoo oo: B< MQqubmHQ zomm£+memnpceum m m. .HV mo pow vmaznvmeosoagoak. on» ,3 , ,VV . . , V Eopm Uganda camounoflznmeHpe to .2. m. info: mo £59900,de mum: 1 a .annwVEV VV 35 1e undeuterated isomer XXVI. The assignment of the auterium to a position ortho to the carbomethoxy group, nile not rigorously confirmable, is supported by the ass spectral peaks mentioned above at m/e lu8, and 120. flat the material is predominantly XXVI is substantiated y the intense peaks at m/e = 163 (P—CH3), 1&7 (P—OCHS, ase), 146 (P—HOCH3), 119 (P-COOCHS) and 118 (P—HCOOCHB). Compare to the mass spectrum of authentic methyl 2,u,6- rimethylbenzoate, Figure 3c in the Appendix.) That the ethyl 2,A,6-trimethylbenzoate derived from XXIII contains ittle deuterium suggests a mechanism for its production onsonant with the proposal earlier put forward. Com— ound XXVI could arise by attack of the 0013 moiety at he position of the deuterated methyl group followed by diSproportionation reaction with a second molecule of sodurene to produce pentamethylbenzene. This reaction cheme is presented below: CD {3 3 CH3 0013 CD H 3 3 A1013 CH3 C 3 col“ CH3 CH3 \\\\\\‘\ 0013 (XXIII) CH3 H CD3 + CD H30 3 CH3 —H+ 3 CH ‘—-—-——”"' CD3 H CH3 CH CD3 3 CH3 36 1e production of compound XXVII is rationalized by a Lmilar mechanism which involves intramolecular migration f the deuterated methyl group prior to disproportion- tion. CD3 CCI3 CCI3 A1013 CH CH3 CH CD3 —————-.n XXIII CC“ —-——- CH3 H3 CH3 Disproportionation 0013 CD3 CD3 CH3 CH3(D3) CH3 CH3 CH CH3 H H CD H 3 CH CH3 L 3 C 3 3 CD3 CD3 CH3 CH3 CH3 CH3 CD3 CH3 CH3 CH3 Fhis mechanism is supported by the observation that the lethyl pentamethylbenzoate derived from XXIII contains luch of the deuterium lost in the disproportionation re- Lction that produces XXVI. The mass spectrum (Figure 2) >f the methyl pentamethylbenzoate derived from XXIII shows molecular ion peaks at m/e = 209 (incorporation of :hree deuterium atoms) and 212 (incorporation of six ieuterium atoms) with the latter peak being about twice as intense as the former. That the material is pre— iominantly XXVIII below is substantiated by intense peaks ...Vr| .. a.) . - .\ . \x. v ... I I a V . . .I \ _. r r . . - \“x n I . x \ . J V omammaocmspm: ucmscmmhdm mam V . . m V V . V. mvl .mV. .m .Nuwcmmcmflhnmemspwhnm w m H mo conmamcumEOLoaVLofinhV 9.5 V Eons... .pwvaumqm wumoncwflhcowmamucom thuwz. mo .EdWonwmm new: .. V ... NWWdouHm _ 38 at m/e = 181 (P-OCH3, base), 180 (P—HOCHB) and 153 (P-COOCH3). There is also some of the methyl pentamethyl— benzoate present containing only three deuterium atoms as evidenced by less intense peaks at mass—to—charge ratios three units less than those listed above. CD3 CH3 CH3 CD3 COOCH3 CH3 (XXVIII) The mass spectrum of the methyl 2,M,6-trimethyl— benzoate (Figure 3) derived from XXIV is unfortunately very poor. The sample was extremely small and subse- quently the pressure in the spectrometer source reservoir dropped during the course of obtaining the spectrum. However, the weak but discernible molecular ion mass peak at 181 units is in accord with the mechanism pro- posed above for the production of this isomer. The mechanism proposed for the production of this pair of disproportionation products in the trichloro- methylation of isodurene is analogous in many respects to that put forward by Dewar (27) for the production of hexamethylbenzene and prehnitenesulfonic acid in the Jacobsen reaction of pentamethylbenzene. These two pro— ducts are, however, only minor products in the V... V. ...uVH . JVV . V . VV. A. . V m.Hw>Hocm:pmz ucmswmmndm mom V .. - .2 . ms .m .Vm .m mammcwthcpoEmsumE m m m. H mo. EOHumH>cmeosoHcloH may . . . . V V .Vm V. V Eopm va>wao opmoncthhszEHhh .0. 2V m Hmnwoz mo EshuomaM .m.mmz V V,.. . :u M.“ n. . V . . V .. V.me... . n. a VV “V V V\ . . V .V .m wham.Hm. . . . HO triChloromethylation of isodurene and attention must be focused upon the two major products, trichloromethyl— isodurene and trichloromethylprehnitene. The production of the major product, trichloro- methylisodurene (isolated as the methyl benzoate) is easily rationalized by the widely accepted mechanism for electrophilic aromatic substitution with, in this case, no rearrangement. This assumption is borne out by examination of the nmr spectrum of the methyl 2,3,“,6- tetramethylbenzoate—6',6',6'-d3 (XXIX) derived from XXIV. CH3 CH3 CH3 CH3 (1) A1013,CC1. CH3 CH3 (2) CH30H COOCH3 CD3 CD3 (XXIV) (XXIX) The spectrum of the unlabeled ester (Figure 8b, Appendix) Shows peaks in the methyl region at r7.92, 17.98, and 18«03 in relative intensities of 2:1:1. The peak at lowest field is assigned to the methyl groups flanking the carbomethoxy group and shifted downfield by mag- netic anisotropy effects of the carbonyl group. This assignment is made on the basis of the nuclear magnetic resonance spectra of the model compounds tabulated in Table IV. These compounds (with the exception of com— pOund H) were chosen because molecular symmetry a m I. moooo I xn .m new m mucsomEoo mo Enhpomam on» on QOmHEmQEoo an moms mpcmEcmHmmmm Ii- 3;. ms; 2: w m mm; mm; 8; 22m Q 2 mm.s ow.» III: pm2 gflwufl m m. mwé mm; mm; pom 1@ m a: ---- 2; pm Q 2 x «yam mum: onpno Hvasmmoe :H powwooqv nmESposspm pesogsoo F .QOHpHmom Hmstm mocMCOmmm mssmHm mMBHm mo H mHmVHosmnmei Mcozvmmnam Home .mb: .w. ..m .mlmCmunmnHznpmc—mppce mm m. N H V..VH0 EOHHMHHEHmEOLOHLoHHH 9t. Eofiw ww>HthV 0 V. cpmowcwfl>numEmhuch Vm..V. 2 ...m. .m flmnuflmz "Ho. Eupuwwam VooEWEOmmm pHHchmszV EmmHopz . . 2 sham? V . . . . 22H 222. .3. u m8 mam mHmzHoc.mLuo: HcmzcmwASmV vsmV mUVs.m .m .m mcmmcwnszquMHuoh um. m .m. H ..mo. EOHHmHmcuoEoEOHonLF wcp EOHM mm>HHoo.. mpmomcwnHzamemppwelm.2 m. m Hmzuo: mo EsHuommm .mmmz .m .wndem DLHwEmHHm91m m. m .H mo VEOHHmHmsumEOHOHLoHHH 05H EOHH ©0>HHwQ .N.Nn meONcwnH>nHmLmHume .mV 3. m w Hmaum: mo. ESHHomam mocmcomom OHHocmmz HmmHosz. 1.. m . a . .. ._ h .w .mhstm VVVVVV. . .3 . V . V V -_ ..vnucO V 2;. meUV M6 The mass spectrum of XXX (Figure 7) is more instructive, however. The parent mass of 195 units bespeaks of the incorporation of 3 deuterium atoms while the absence of strong ortho effect peaks at m/e = 162 (P-DOCHa) and 13h (P-DCOOCHB) shows that there is little if any deuterium ortho to the carbomethoxy group° Clearly the data ob- tained for compound XXIX are free from the ambiguities in that obtained for XXX, but taken as a whole the re- sults are in agreement with the mechanism proposed for the production of trichloromethylisodurene from isodurene. The most interesting product from the trichloro— methylation of isodurene is trichloromethylprehniteneo The structure of the products derived from labeled start- ing materials seem to suggest that the production of tri— chloromethylprehnitene results from attack of the electro- phile at the 5—position in isodurene followed by a 1,2- shift of methyl and deprotonationo CH CH3 CH3 3 V CH3 A1013 CH CH3 ____> 0014 H H3 CH3 CH3 0013 0013 C 3 CH3 CH3 0013 h‘ ”H . H .me>Hocmspmz pawswmwhsm mam. I.. me .NI .NI.NI mcmwcwna>cpm6wppwh .m m N .H. mo coauma>nuoeoaoazoape ocu:.,w . - mmJ..,I .uIflws. . Eopm ©o>apmm mumomconahnpwamppme m. z m N H>zpsz mo Espvooam mm.mz . I I IN opswam.. ‘wq- MK 48 The nmr spectrum of the methyl 2,3,u,5—tetramethyl— benzoate (Figure 8) derived from XXIV indicates the product to be XXXI. CH3 CH3 CH3 CH3 (1) A101,,CCl, CH3 H3 (2) CH30H CD3 CD3 COOCH3 jH (XXIV) (XXXI) The spectrum of the unlabeled isomer (Figure 16b, Appendix) shows a three-proton signal at I7.55 which, on the basis of the data in Table IV, may be assigned to the methyl group ortho to the ester function, The nmr spectrum (Figure 8) of compound XXXI shows this peak to be essentially absent. The more revealing mass spectrum (Figure 9) shows, however, a peak at m/e = 163 (P-HOCHB) in addition to the solely expected ortho effect peak at 162 (P-DOCH3)° Although this could arise from scrambling of the deuterium label by some unknown mechanism, it is tempting to rationalize its presence by fragmentation of a specie such as XXXII, CH3 CD3 COOCH3 (XXXII) 49, In: . we . mwa .m ..m .mecmNcmnH>meEmpume m m. N H mo coapmH>LPwEopoHnoape may Eonw ©w>ahwa IL. L mammaocmcpw: pcmscwmnzm cam mumoucmnathMEMmeetm 3. .m. 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EEEEEIEEEEEEEIEEEII MEI . t -. ~ EEEEE lEEEgEEEIIEIEEEEE llll -- I- , -‘ EIIEEEEEEEEEEEEIHEEEE ll!!!“ I - ~ ~ . ' III II EEEEEE “E117? .713 E...‘ I . . - . II E the Trichloromethylation of‘1,2,8,SéTetramethylbenze'ne—ESYE,5.' ,IS'L-ds and . 5 {A . Finn's _ . EIEEE EH3 .. . ‘v . I E . _ .- . I. ' 11'.‘.3’ - H EIIE EIIE; EEEE I :1" I, p . "Q I I'A' . I - i U . . EIIIII EEEEEEEEEEE EEI EEE IIIIIIIIIIIEIEEEEEIEE E ‘ ‘ ‘ Subsequent Methanolysis E V E II? . _ .E I?" 51 Ihich could be produced by attack of CCl3 at position 4 Ln the labeled isodurene followed by two successive 1,2- Ihifts to relieve steric strain. CH3 c01: 0013 CD3 0013 In D3 ,. (XXIV) “CH3 CH3 0013 0013 CD3 CH3 CH3 CH3 CD3 CCl3 The methyl 2,3,U,S—tetramethylbenzoate derived from isodurene labeled at the 2—position is predominantly the ‘ u-labeled ester XXXIII. 52 CD3 CD3 (1) A101 001 CH3 CH3 CH3 3’ 1+ CH3 -—————————a-. (2) CH3OH CH3 CH3 COOCH3 (XXIII) (XXXIII) The resonance signal at 17.8u in the spectrum of the un— labeled material (Figure 16b, Appendix) can reasonably be assigned to the methyl groups at positions U and 5. In the spectrum of XXXIII (Figure 10) this peak is diminished to almost one-half the intensity of that in the spectrum of the unlabeled isomer. The mass spectrum of XXXIII (Figure 11) shows all of the expected frag- mentation ions with peaks at m/e = 195 (P), 180 (P-CH3), 164 (P—OCHS, base), and 163 (P-HOCH3). There is no evi— dence of an ortho effect due to loss of DOCH3 which is in accord with the structural assignment of XXXIII° The small amount of methyl 2,3,5,6-tetramethyl- benzoate derived from isodurene could be explained as arising from attack of the 0013 electrophile at either of the equivalent positions 1 or 3 in isodurene followed by a 1,2—methyl shift and deprotonation. H 3 .....6.... ...]... .. . . ...... . , . . .. mammaosmnvoz pc0dcwmnsm “Nam .. .. ... . .. . .. . 1 . .. . J 1.... ..... walk .....N. .NamchE0§>Eu.0Ewhpmenm m... ..N. A we noHumamEpmaoaoanoaph 0:“ Eofim pwbapao .. .. .. pmoucmflzfiwsmfiweum .2 .m..... N.. 150:. Mo 52.58% mongomwmdflucmmz human? . ,. .. . .. .. 031 f me>Hoc0Ep02 ucmzv0mnzm . . , h. ... mam m.pu.N ...N. .NnmcmucoEH>EumEmupme .m m .N H w.o. coaumfiaEpmsopanoHpe .mEp .Eonu p0>EL0Q 0pm0NE0EH>Epwzmpuwelm E. .m.. N H>Ep0z mo E:Eu.oomm .m.wmz .. H... .HH 03mm...» 55 CH3 CH3 CH3 CH3 CH3 CH3 A1013 CH3 01 CH3 0013 3““’* CH 001, H CH3 0 3 CH3 -H+ CH3 CH3 CH3 COOCH3 CH3 0013 +—-———— CH3 CH30H CH3 CH3 CH3 (XXXIV) Unfortunately, as stated before, it was not possible to separate XXXIV from its isomers in the glc columns em— ployed in the isolation of the other isomers. Thus, the structure of labeled XXXIV could not be ascertained to test the validity of the above mechanism, However, it seems reasonable in light of the previous arguments that the above mechanism could account for the small amount of XXXIV observed. It appears that the mixtures of products arising from the trichloromethylation of the four tetrasubsti— tuted benzenes studied result from a series of competing 56 reactions involving attack at each position of the sub- ,strate ring followed by deprotonation or methyl migration ’and deprotonation° The product mixture composition can then be viewed as reflecting the relative magnitudes of :the partial rate factors for attack at each site° These ‘in turn are affected by the activation energy requirement in reaching transition states in each case. Unfortunately there is no convenient method of predicting the relative {M ‘ stabilities of the transition states leading to each of ‘ the products. However, carbonium ion theory does provide a means of evaluating the relative stabilities of the re— active intermediates. Although there are objections (61) ‘to the use of the reactive intermediates rather than the transition states for this type of argument, the con- clusions drawn from such a treatment are probably valid. When this tool is applied to the problem in question, it is easy to rationalize the product mixture compositions. This has been done for the case of isodurene and the re- active intermediates in each case are depicted in chart form on the next pagea The intermediate arising from attack at the u or 6 position (XXXVII) is stabilized by distribution of the charge in the ring to carbon atoms bearing methyl substi- tuents. On this basis one might expect a priori that the major product would be the one resulting from this intermediate. There is, however, some steric hindrance pQ0Hm>H5U0 mpfl so +maoo n +x 1 UHHH>xxx EHHH>xxx «HHH>xxx x soapflmoa m .. 02.5er Caisson SHEEN - +x ‘ I ADE i Q. x x x EONENmOQ m :1... AI... 1% x E w WE u l + COHpHmom m m H 0H>xxx EH>xxx 0H>xxx . +x N COHpHmoo m so H 1 x3 z x3 o>xxx D>xxx m>xxx .1 Q 3 Q 58 1to the formation of XXXVII. This destabilizes the inter- mediate bringing it closer in energy to less hindered but ‘also less charge—stabilized species as XXXVIII. This re- ‘sults in greater competition for the starting material by the reaction leading through XXVIII. Using the same argu- ‘ment, the product arising from XXXVI might also be ex— Ipected to be relatively abundant. However, the con- Lsumption of XXXVI is through a disproportionation re- .3 .action with correspondingly stringent enthalpy and entropy ‘ Lrequirements. This militates against the loss of much (starting material through this path. The formation of XXXV is both sterically and ‘ electronically unfavorable. When the 2—position of the starting material is substituted with an inductively electron—withdrawing halo- gen atom, structures XXXV, XXXVI and XXXVIII are de- stabilized, although apparently the last to not as great an extent. The large amount of product arising from XXXVIII when the substituent on the 2—position is fluorine is another example of the tendency of fluorine to acti— vate positions para to itself in electrophilic aromatic substitutions (62)- SYNTHETIC SEQUENCES A large number of compounds were synthesized in :onnection with this research, some of which were pre— Iiously unknown. Equations showing the structures of :hese compounds have been omitted from the text of the Experimental to avoid clutter. Those equations are produced below in chart form to give the reader a quick overview of the synthetic sequences employed. Each compound is designated by a combination of letters and numbers which correspond to the position of the synthesis in the outline of the Experimental. 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