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Signature Redacted Signature of Author DIEJ:$-ALDER REACTIONS OF ORGANOTIN ACETYLlDES AND THE CHEMISTRY OF THE ADDUCTS by AN.I'HONI BA.Sil, EVNIN A.B., Princeton University (1962) SUIMITTED IN PARTr.AL FULFILIMEN.I' OF THE REQUIR»mN.I'S FOR THE DEGREE OF DOCTOR OF PHil.00 OPHY at the MASSACHUSETI'S INSTITUTE OF TECHNOLOGY July, 1966 /I - /7 Signature redacted Signature of Author _"___ """'De_patj;...:.. · - . .,.._m-e-~-1--1,..,,.f"""'Ch,,.,..;..emi_.s.,..tr-y-,-J""'"uJ.y~'""'2""'6'""'", ~1"'!096""6.-- Certified by Signature redacted ___, -s--....c- ·--c --. - .--x-,---,.-Th-es-i-s-s,,...u_pe_rv__is_o_r __ Accepted by Sign_atur~ .reda~~ed Chairman, Departmen-f,i. Committee on Graduate Students -4 77 Massachusetts Avenue Cambridge, MA 02139 MITLibrares hftp://Iibraries.mit.edu/ask DISCLAIMER NOTICE Due to the condition of the original material, there are unavoidable flaws in this reproduction. We have made every effort possible to provide you with the best copy available. Thank you. Despite pagination irregularities, this is the most complete copy available. No page number 9 Page between pages numbered 14 and 15 is unnumbered. A 038 This Doctoral thesis has been examined by a comnittee of the Department of Chemistry as follows: Signature Redacted Prof. Glenn A. Berchtold (Chairman) Signature Redacted Prof. Dietmar Seyferth (Thesis Supervisor) Prof,Po GrgGeorge IM..Witesides_______________________ iSignature Redacted I DIELS-ALDER REACTIONS C RGANOTI ACETYLDES AND TME CHEMISTRY GE THE ADDUCTS by Anthony B. Evnin Submitted to the Department of Chemistry in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy ABSTRACT Chapter I. Diels-Alder Reactions of Organotin Acetylides with Highly Chlorinated Cyclopentadienes and the Chemistry of the Adducts The Diels-Alder reaction of organotin acetylides LRC m-Sn (CH 3 )3 , R (CH 3) 3Sn-, 0-, CH 3-] gives bicyclo[2.2.1]hepta-2,5-dienes, typical- ly in 50-70% yields. The carbon-tin bonds in t he adducts are readily cleaved by electrophiles, without rearrangement of the carbon skeleton, to give novel, highly halogenated bicyclo[2.2.1]hepta-2,5-dienes. One of these,2,3-dibromo-l,4,5,6,7,7-hexachlorobicyclo[2.2.1]hepta- 2,5-diene, was converted by bromine-metal exchange, to its 2-lithio derivative, which exhibits unusual stability for a P-balolithium system. The Diels-Alder reaction of 1,2,3,4-tetrachloro-5,5-dimethoxy- cyclopentadiene and bis(trimethyltin)acetylene, which yields 1,2-bis- (trimethyltin)tetrachlorobenzene, was also examined. Chapter II. Diels-Alder Reactions of a-Pyrones and Bis(trimethyltin- acetylene and the Chemistry of the Adducts The Diels-Alder reaction of a-pyrone and several of its analogs (5-carbomethoxy-, 5-methyl- and 4,6-dimethy-a-pyrone) with bis(trimethyltin)acetylene to produce o-bis(trimethyltin)benzenes in good yields is described. The reaction affords a route to novel tin-substituted aromatic compgunds. The utility of a-pyrones in a general, one-step synthesis of benzenoid systems is discussed. The enhanced reactivity towards bis(trimethyltin)acetylene of a- pyrones subitituted with electron withdrawing groups is established -4- and discussed in terms of current theories of the Diels-Alder reac- tion. Chapter III. Photochemistry of Unsaturated Organotin Compounds Irradiation of 2,3-bis(trimetbyltin) -1,4,5,6,7,7-hexa- chlorobicyclo[2.2.1]hepta-2, 5-diene and of ,2-(trimethyltin)-1,4,,5,6, 7,7- herachloro-3-metbylbicyclo[2.2.1]hepta-2,5-diene converts them to t he corresponding quadricyclenes. This constitutes one of the first e xpmples of photoisomerization of a main group organometallic com- pound. Protodestannation of these tin-substituted quadricyclenes occurs without rearrangement or carbon-carbon bond cleavage. aromodestannation was found to be more complex' and evidence is present- ed for the involvement of free radical intermediates in this case. Irradiation of o-bis(trimetbyltin)benzene leads only to dissociation of the carbon-tin bond; no isomerization of the aromatic nucleus was observed. Chapter IV. Thermal Decompoition of 2-Metallo-l,4,5,6,7,7-exachloro- bigyclo[2.2.1]hepta-2 5-dienes and o-Halo(trimethyl- tin)aromatics, Thermal decomposition of 2-metallo-l,4,5,6,7,7-hexa- chlorobtcyclo[2.2.1]hepta-2,5-dienes (M = Sn, Hg) in the melt at 2300 yielded the mixture of products expected from homolytic scission of the carbon-metal bond and subsequent reactios of the rragments. The mechanism is discussed in detail. Similar heating of o-halo- (trimethylti)ensene syatemr dea not result in earbon-tin~homolysis; instead, coupling reactions to foam (2-haloe-2-biphenylyl)trimethyl- tin derivatives or- isproportionation of the tin compound occur. Evidence is presnte bat similar intermediates are involved in the formation of these two types of products. Thesis S pervisbrt Dietmar Seyferth Title: Profddsde Of Chemistry U ~- TABLE OF COINETS Page IInRODUCTION...... ** ... *........* .. s.. ....... *.. ....... ... 10 CHAPTER I. THE DIELS-ALIER REACTIO14 OF ORGANOTIN ACETYLIDES WITH HIGHLY CHLORINATED CYCLOPENTADTENES........... DISCUSSION AND E 15 EX R3ENTAL .. .. ... .... ...... ..0 0.... ... - 3 Preparation of Bis(trimethyltin) acetylene. ............... 36 Preparation of Propynyltrimethyltin and (Phenyl- ethyny)trietbhritiri. ......... y........................ 38 Diels-Aider Beaction of Bis(trimethyltin)acetylene ani Hecxachlrocyclopentadiene: Preparation ot 2,3-Bis(tr methyltin)-1,4, 5,6,7,7-hexachlorobicyclO- [2..2.1hep a 2,5-diene- ------- - ---------.------------, 40 Diels-Alder Reaction of Propynyltrimethyltin and fexa- chloroeyclopentadiene: Preparation of 2- (rimethyl- tin)-1,4, 5,6, 7-hexachloro--3-methibiqyClo[2.2.1] - hepta-2,5-diene- - . -00-*-- -..-- --.-e- - --- - --- -- -- -- -- 42 Diels-Alder Reaction of (PhenylethynylJ)trimethyLtin and 14xachlorocyclopentadiene: Preparation of 2-(Tri- methyltin) -1,4,5,6,7, 7-hexachloro-$--1IY bicyclo [E.2.1)hepta-2,5-diene----------------------------------0*0 43 Electlea lic oDsstamn of 2.3-{BisriiyetbxJtin)- 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]epta-2 3-diene: Preparation of Octacgi1orobicyclo[2.2.1]hepta-2,5- diene, 2, 3-Dibromo-1, 4,5,6,7, 7-hexachlorobiayclo- (2.2.1]hepta-2,5-diene and 1,2,3,4,7,7-Hexachloro- bicyclo( 2.2.l]hepta-2,5-diezie'1.*00*.- - 0 0 0 -440'D ----0 a 0 0 a Electrophilic Destannation of 2-(T imethyltin) 1,4,5 6,7, 7-hexachloro-3- methylbicyclo[2.2.1Jhept#-2,5- diene: Preparation of Heptachlqro-&-methylbicyclo- [2.2.1]hepta-2,5-diene, 2-Bramo-,4,5,6,7,7-hexachloro- 3--methylbicyclo[2.2.1]hepta-2,5-diene and 1,2,3,4,7, 7-HexachLo'-5-methylbiyclo[2.2.l]hepta-2,5-diene..-.- 47 -6- Page Unsuccessfu4l Attempts at Monohalodestannation of 2,3- Bis(trimethyltin) -1,4,5,6,7, 7-hexachlorobicyclo- [2.2.1]hepta-2,5-diene. - -..-*. 0 ---- 000 0 - 00 00--0 49 Reaction of n-Butyllithium with 2,3-Dibromo-l,4, 5,6,7,7- hexachlorobicyclo[2.2.1]hepta-2, 5-diene: Preparation of 2-Lithio-3-bromo-1,4, 5,6,7,7-hexachiorobicyclo- [2.2.1]hepta-2,5-diene..................-......... 51 Reactions of 2-Lithio-3-bromo-1,4,5,6,7, 7-hexachioro bicyclo[2.2.1]hepta-2,5-diene: Preparation of: 2-Biroo-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]- hepta-2, 5-diene.........0...---------- - ---- 54 2-(Trimethyltin) -3-bromo-l, 4, 5,6,7,7-hexachloro- bicyclo[2.2.1]hepta-2,5-diene..............0000. 55 2-Bromoheptachlorobicyclo[2.2.1]hepta-2,5-diene... 57 Bis(2-bromo-1,4,5,6,7,7-hexachlorobicycio[2.2.1]- hepta-2,5-dienyl)mercury........ 58 2-Carbomethoxy-3-bromo-1,4,5 ,6,7,7-hexachloro- bicyclo[2.2.1]hepta-2,5-diene ......------------- 60 Attempted Preparation of 2,3-Dilithio-1,4,5,6, 7,7-hexa- chlorobicyclo[2.2.1]hepta-2,5-diene by Halogen- Metal Exchange ..... ......... ..- .---- 61 Stability of 2-Lithio-3-bromo-1,4, 5,6,7,7-hexachloro- bicyclo[2.2.1]hepta-2,5-diene in Ether................ 62 Decomposition of 2-Lithio-3-bromo-1, 4,5,6,7, 7-hexa- chlorobicyclo[2.2.1]hepta-2, 5-dienes in the Presence of 2,5-Diphenylisobenzofuran and Furan........ 64 Reaction of n-Butyllithium with Octachlorobicyclo- ..-.. 66 (2.2.1]hepta-2,5-diene........--.- 00---. Diels-Alder Reaction of Bis(trimethyltin)acetylene and 1,2,3,4-Tetrachloro-5,5-dimethaxycyclopentadiene: Preparation of 1,2-Bis(trimethyltin)tetrachlorobenzene. 68 CHAPTER II. DIELS-ALDER REACTI0BS CF a-PYRONES WITH BIS- (TRD4ETHYLTIN)ACETYIENE. 000000. 0.0...0.000 74 DISCUSSION AND RESULTS.-0.......... -...... .. 0 75 EXPER3MENTAL Preparation of a-Pyrone.*.*.ooooooooo....... - 0. -- -- 90 Preparation of Substituted a-Pyrones.....0..... --. 92 -1 -7- Diels-Alder Reaction of a-Pyrone and Bis(trimethyl)- acetylene: Preparation of o-Bis(trimethyltin)benzene... 93 Diels-Alder Reaction of 5-Carbomethoxy-a-Pyrone and 1Bis- (trimethyltin)acetylene: Preparation of Methyl 3,4- 94 Bis(trimethyltin)benzoate......................0......0 Diels-Alder Reaction of 5-Methyl-a-Pyrone and Bis(tri- methyltin) acetylene: Preparation of 3, 4-Bis (tri- methyltin) toluene--000 - * 0 - 0.-.-. .... .... 0.0* 0 00. 95 Attempted Diels-Alder Reaction of 4,6-Dimethyl-a-Pyrone and Bis(trimethyltin)acetylene ................... 96 Diels-Alder Reaction of a-Pyrone and (Phenylethynyl)tri- amethyltin: Preparation of (2-Bipheoylyl) trimethyt. ... 97 Competition Reactions Between a-Pyrone and 5-Carbometh- oxy-a-Pyrone and a-Pyrone and 5-Methyl-a-Pyrone for 1is(trimethyltin)acetylene.............. 0000 ..... 98 Iododestannation of o-Bis (trimethyltin)benzene: Prepara- tion of o- Iodo(triiiethyltin)benzene.. .0 .. ........ o. 100 lododestannation of Methyl 3,4-Sis(trimethyltin)benzo- ate: Preparation of Methyl 3-1odo-_4-(trimethyltin)- benzoate and Methyl 4- Iodo-3-(trimethyltin)benzoate ..... 101 Iododestannation of(2-BiphenylyJ~rimethyltin: Prepara- tion of 2-Iodobiphenyl.......0....0...0....-00.0.0-000.
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