The University of British Columbia FACULTY OF GRADUATE STUDIES PROGRAMME OF THE FINAL ORAL EXAMINATION FOR THE DEGREE OF DOCTOR OF PHILOSOPHY OF DAVID STUART DAWSON B. sc, M.Sc,, University of British Columbia MONDAY, JUNE 12, at 3:30 P.M. IN ROOM 261, CHEMISTRY BUILDING COMMITTEE IN CHARGE Chairman: B. N. Moyls E. Peters - D.E. McGreer C. A. McDowell N.L. Paddock A. Storr . G.B. Porter External Examiner: H.J. Emeleus University Chemical Laboratory Lensfield Road Cambridge, England Research Supervisor: W.R. Cullen REACTIONS OF SOME UNSATURATED FLUOROCARBON DERIVATIVES WITH ORGANO COMPOUNDS OF PHOSPHOROUS AND NITROGEN ABSTRACT Perfluorocyclobutene and 1,2-dichlorotetrafluoro- cylobutene react readily with diethylphosphine at 20° to give unstable mono-subs'titution products, 1-diethyl- phosphino-2-halotetrafluorocyclobutenes. With tetra- methyldiphosphine, low yields of 1,2-bis(dimethylphos- phino)tetrafluorocyclobutene and trifluorodimethylphos- phorane are obtained from the chloro- and perfluoro- butenes respectively. Diphenylphosphine also gives the 1,2-disubstituted product at.20°, from perfluorocyclo• butene only. This olefin interacts with tetraphenyl- diphosphine (130°) to give 1-diphenylphosphinotrifluoro- cyclobutenone (from 95% ethanol). Under identical conditions the chloro-butene reacts with the phenyl- phosphines to give trifluorodiphenylphosphorane and fluorodiphenylphosphine oxide. Tetrakis (trifluoro- methyl)diphosphine on heating or ultra-violet irradia• tion reacts only very slightly, while bis(trifluoro- methyl)phosphine is essentially inert towards the cyclobutenes. Dimethylamine readily adds to hexafluorobutyne-2 at 20°to give the 1:1 adduct, 2-dimethylamino-3-H-hexa- fluorobutene-2, the ratio of trans:cis isomers being 6.2:1. -.The cis isomer is converted by distillation, but not by heating in a sealed tube, to the trans form. This latter isomer quickly achieves an equilibrium with the cis configuration on exposure to the air;; at equi• librium, trans:cis 1.6:1. Hexafluorobutyne-2 reacts vigorously at 20° with a trimethylamine-water mixture. The major products of the complex reaction are a bis(hex- afluorobutenyl) ether and trans-3-H-heptafluorobutene-2. When the reaction mixture is permitted to reach room temperature only slowly, the ether predominates. In the absence of water a high polymer of the butyne is slowly deposited. Chlorodimethylamine requires heating or ultra-violet irradiation to react with the butyne. The reaction is complex. At 85° (also on1 irradiation), the major product is the 1:1 adduct (1007. cis) ; at 139°, trans-2-chloro-3-H-hexaf luoro• butene-2 predominates. Prolonged ultra-violet irradiation of a bis(tri- fluoromethyl)phosphine-hexafluorobutyne-2 mixture affords a mixture of 1:1 and 2:1 adducts. The expected 1,1,1,4, 4,4-hexafluorobut-2-enyl derivatives are obtained from the acetylene and diethylphosphine, "diphenylphosphine and tetraphenyldiphosphine (130°) „ Tetramethy.ldiphosphine gives a low yield of methyldifluorophosphine oxide. Triphenylphosphine vigorously catalyzes the'polymeriz• ation of the butyne at -78°. Chlorodimethylphosphine and hexafluorobutyne-2 afford trans-3-H-2-chlorohexa- fluorobutene-2 and trifluorodimethylphosphorane, while chlorodimethylphosphine sulfide does not react on heating (106°) or ultra-violet irradiation. Tetra- methyldiphosphine disulfide and iodine afford a loosely- bound 1:1 complex at 20° in the absence of excess iodine. Trifluoromethyl iodide does not react with the disulfide at 104° and only slightly on prolonged ultra-violet irradiation. Dimethylphosphine readily adds to hexafluoroacetone and 1,1,1-trifluoroacetone, giving the 2-dimethylphos- phino-isopropanols. The reaction with hexafluoroacetone also gives a 1:3 phosphineacetone adduct.' The product from T,3-dichlorotetrafluoroacetone decomposes violently on reaching room temperature. The reactions of these fluorinated ketones with diphenylphosphine are more complex. The products include a mixture of 1:1 adducts; namely, 2-diphenylphosphino-isopropanols and isopropyl- diphenylphosphine oxides. The latter probably are a result of an Arbuzov rearrangement of isopropoxydiphenyl- phosphines. Tetramethyldiphosphine and hexafluoro• acetone give a 1:3 adduct along with the 1:3 dimethyl• phosphine -hexaf luoroacetone adduct-. GRADUATE STUDIES Field of Study: Chemistry Topics in Physical Chemistry A.V. Bree,J.A.R. Coope Seminar in Chemistry W.A. Bryce Topics in Inorganic Chemistry N. Bartlett W.R... Cullen The Chemistry of Organometallic Compounds H.C. Clark Topics in Organic Chemistry F. McCapra,A.I. Scott, J.P. Kutney Recent Synthetic Methods in G.G.S. Dutton, Organic Chemistry A. Rosenthal Spectroscopy and Molecular Structure B.A. Dunell, A.V. Bree,C. Reid Advanced Inorganic Chemistry Organic Reaction Mechanism B.R. James,G.B. Porter Physical Organic Chemistry L.D. Hall,D.E. McGreer, T. Money, F. McCapra Organic Reaction Mechanisms R.E. Pincock Related Studies: Organic Medicinal Products T.H. Brown PUBLICATIONS M.M. Baig, W.R. Cullen and D.S. Dawson, Reaction of Iodomethane and Tertiary Arsine Mercuric Iodide Complexes, Can. J. Chem. 40, 46 (1962) W.R. Cullen, D.S. Dawson, N.K. Hota and G.E. Styan, Some New Derivatives of. Dimethylarsine, Chemistry and Industry 983 (1963) W.R. Cullen, D.S. Dawson and P.S. Dhaliwal, Cyclobutenyl Derivatives of Phosphorus and Sulphur, Can. J. Chem. 45, 683 (1967) REACTIONS OP SOME•UNSATURATED FLUOROCARBON DERIVATIVES WITH ORGANO COMPOUNDS OF PHOSPHORUS AND NITROGEN by DAVID S. DAWSON B.Sc, University of British Columbia, 1961 M.Sc, University of British Columbia, 1964 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY In the Department of Chemistry We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA April 1967 In presenting this, thesis in partial fulfilment of the requirements for an advanced degree at the University of -British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted' by the Head of my Department or by his represen• tatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. for David Dawson Department nf Chemistry The University of British Columbia Vancouver 8, Canada Date January 18, 1968 i ABSTRACT Perfluorocyclobutene and 1,2-dichlorotetrafluorocylobutene react readily with diethylph.osph.ine at 20° to give unstable mono- substitution products, l-diethylphosphino-2-halotetrafluorocy- clobutenes. With tetramethyldiphosphine, low yields of 1,2- bis(dimethylphosphino)tetrafluorocyclobutene and trifluorodi- methylphosphorane are obtained from the chloro- and perfluoro- butenes respectively. Diphenylphosphine also gives the 1,2- disubstituted product at 20°, from perfluorocyclobutene only. This- olefin interacts with te traphenyldi'phosphine (130 ) to give Irdiphenylphosphinotrlfluorocyclobutenone (from 95$ ethanol). Under identical conditions the chloro-butene reacts with the phenyl-phosphines to give trifluorodiphehylphosphorane and fluoro- diphenylphosphine oxide, Tetrakis (trif luor'omethyl) diphosphlne on heating or ultra-violet irradiation reacts only very slightly, while bis(trifluoromethyl)phosphine is essentially inert to• wards the cyclobutenes. Dimethylamine readily adds to hexafluorobutyne-2 at 20° to give the lsl adduct, 2=dimethylamino-3-H-hexafluorobutene-2, the ratio of trans:cis Isomers being 6.2sl. The cis isomer Is converted by distillation,? but not by heating in a sealed tube, to the trans form. This latter isomer quickly achieves an equil• ibrium with the cis configuration on exposure to the afrj at equilibriums transscis^1.6;1. Hexafluorobutyne-2 reacts vig• orously at 20° with a trimethylamine-water mixture. The major products of the complex reaction are a bis(hexafluorobutenyl) ether and trans-3-H-heptafluorobutene-2. When the reaction mix• ture is permitted to reach room temperature only-slowly, the " ether predominates. In the absence of water a high polymer of the butyne is slowly deposited. Chlorodimethylamine requires heating or ultra-violet irradiation to react with the butyne. The reaction is complex. At 85° • (also on irradiation), the major product is the 1°1 adduct (100$ cis)j at 139°, trans-2-chloro~3- H-hexafluorobutene-2 predominates. Prolonged ultra-violet irradiation of a bis(trifluorometh- yl)phosphine-hexafluorobutyne-2 mixture affords a mixture of 1:1 and 2sl adducts. The expected l,l,l,4,4,4-hexafluorobut-2-enyl derivatives, are obtained from the acetylene and diethylphosphine, diphenylphosphine and tetraphenyldiphosphine (130°). Tetra- methyldiphosphine gives a low yield of methyldifluorophosphine oxide. Triphenylphosphine vigorously catalyzes the polymeriz• ation of the butyne at =-78°. Chloro dime thy Iphosphine and hexa- fluorobutyne-2 afford trans-3-H-2-chlorohexafluorobutene-2 and trifluorodimethylphosphorane, while chlorodimethy Iphosphine sul• fide does not react on heating (106°) or ultra-violet irradiation Tetramethyldiphosphine disulfide and iodine afford a loosely- bound lsl complex at 20° in the absence of excess iodine. Tri- fluoromethyl iodide does not react with the disulfide at 104° and only slightly on prolonged ultra-violet irradiation. DimethyIphosphine readily adds to hexafluoroacetone and lsl, trifluoroaeetone, giving the 2~dimethylphosphino~Isopropanols. The reaction