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Some reactions of tetramethyldiarsine and related compounds Hota, Nalina Kanta 1963

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SOME REACTIONS OF TETRAMETRTIDIARSINE AND RELATED COMPOUNDS by N.alini K.. Hot a A THESIS SUBMITTED IN. PARTIAL FULFILMENT OF THE REQUIREMENTS FOP. THE DEGREE OF MASTER OF SCIENCE i n the Department of Chemistry We accept t h i s thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA June, 1963 In presenting t h i s t h e s i s i n p a r t i a l f u l f i l m e n t of the requirements for an advanced degree at the U n i v e r s i t y of B r i t i s h Columbia, I agree that the L i b r a r y s h a l l make i t freely-a v a i l a b l e for reference and study. I f u r t h e r agree that per-mission for extensive copying of t h i s t h e s i s for. s c h o l a r l y purposes may be granted by the Head of my Department or by h i s representatives. I t i s understood that copying, or p u b l i -c a t i o n of t h i s t h e s i s for f i n a n c i a l gain s h a l l not be allowed without my w r i t t e n permission. Department of (^Jj***^*^*^ • The U n i v e r s i t y of B r i t i s h Columbia,. Vancouver 8, Canada. Date SU*^ • - i -• ABSTRACT Tetramethyldiarsine Is found to add across the double bond of f l u o r o b l e f i n s of the type CF2=CFX (X = F , C l , B r ) , 'to give addition-products. Thus 1:1 adducts, i . e . (CHg)pAs-CFg-CFX-AsCCHg)2, are obtained i n the r e a c t i o n s of t e t r a m e t h y l d i a r s i n e and CF^CFX (X = CI,Br). The r e a c t i o n of te t r a m e t h y l d i a r s i n e and t e t r a f l u o r o e t h y l -ene, however, gives (CH 3) 2Aa-(CF 2-CF 2)^-As(CH 3) 2, a 1:4 adduct. I o d o t r i f l u o r o e t h y l e n e and te t r a m e t h y l d i a r s i n e r e a c t to give an ad-duct which Is unstable i n a i r , but t h i s r e a c t i o n y i e l d s dimethy1-p e r f l u o r o v i n y l a r s i n e , t b.p. 71°. The above arsine i s a l s o prep-ared by the r e a c t i o n of iododimethylarsine and i o d o t r i f l u o r o e t h -ylene i n the presence of mercury. Tetramethyldiarsine does not react w i t h ethylene at 20°.. Bromotrifluoroethylene does not give an a d d i t i o n product w i t h t e t r a k i s C t r i f l u o r o m e t h y D d i a r s i n e . Hexafluoro—2-butyne r e a c t s w i t h t e t r a m e t h y l d i a r s i n e a t 20° to y i e l d a 1:1 adduct,, t r a n s - l , 2 - b i s ( d i m e t h y l a r s i n Q ) - l , 2 - b i s ( t r I -fluoromethyl)ethylene. T e t r a k i s ( t r r f l u o r o m e t h y l ) d i a r s i n e and arsenobenzene do not re a c t w i t h hexafluoro-2—butyne to give adducts. Io.dotrifluoromethane reacts w i t h arsenobenzene to produce i o d o p h e n y l t r i f l u o r o m e t h y l a r s i n e , p h e r r / l b i s ( t r i f luorome t h y l ) a r s i n e and pheny I d l i o d oar s i n e . The mechanism, of t h i s r e a c t i o n has been, suggested. 'The i o d o p h e n y l t r i f luoromethylarsine r e a c t s w i t h s i l v e r c h l o r i d e to y i e l d c h l o r o p h e n y l t r i f l u o r o m e t h y l a r s i n e . The c h l o r o -arsine and b i s ( t r i f l u o r o m e t h y l ) a r s i n e r e a c t w i t h the e l i m i n a t i o n of .hydrogen c h l o r i d e to form a d i a r s i n e , which Is be l i e v e d to be the symmetrical 1,2-b i s ( p h e n y l ) - ! , 2-b i s ( t r i f luorome thyl.) d i a r s i n e . This same d i a r s i n e i s probably formed by the coupling of two iodo-p h e n y l t r i f luoromethylarsine molecules i n the presence of mercury. P'aranitroarsenobenzene r e a c t s w i t h iodotrifluoromethane w i t h ex-i i -p l o s i v e v i o l e n c e . Trimethylarsine does not undergo exchange r e a c t i o n w i t h bromotrifluoroethylene to give d i m e t h y l p e r f l u o r o v i n y l a r s i n e . Hexafluoro-2-butyne does not give an a d d i t i o n compound w i t h iodo— dimethylarsine. T e t r a k i s ( t r i f l u o r o m e t h y l ) d i p h o s p h i n e f a i l s to y i e l d adduct w i t h bromotrifluoroethylene at 120°. Hexafluoro-2-butyne a l s o does not give adducts with. t e t r a k i s ( t r i f l u o r o m e t h y l ) d i p h o s p h i n e , hexa-p h e n y l d i t i n and h e x a b u t y l d i t i n . - i i i -TABLE OF CONTENTS Page ABSTRACT i ACTCNOVi/LEDGEMENT', ;.Y INTRODUCTION 1 EXPERIMENTAL. 3 Section A: Reactions of Tetramethyldiarsine (Cacodyl) and Tetrakis(trifluoromethyl)diarsine (Perfluorocacodyl) 4 with. Olefins and Hexafluoro-2—butyne Preparation of Tetramethyldiarsine 4. ( i ) Reaction of Cacodyl with Bromotrifluoroethylene:-Synthesis of 2-Bromo—1,2-bis(dimethylarsino)-l,,l , 2 - 4 trifluoroethane ( i i ) Reaction of Cacodyl. with Chlorotrifluoroethylene 5 ( i i i ) Reaction of Cacodyl with Tetrafluoroethylene 6 (Iv) Reaction of Cacodyl with Iodotrifluoroethylene 7 (v) Reaction of Cacodyl with Ethylene 8 (vi) . Reaction of Perf luorocacodyl with Bromotr i f luoroethylene 8 Section, B;. Reactions of Diarsines with Hexaflu<sa?o-2-butyne 9 ( i ) Reaction'of Cacodyl with Hexafluoro-2—butyne 9 ( I i ) Reaction of Perf luorocacodyl with Hexaf luoro-2-butyne 11. ( i i i ) Reaction of Arsenobenzene with Hexafluoro-2-butyne 11 Section C: Reactions of Arsenobenzenes with T r i f l u o r o -iodomethane. 12 (I)- Reaction of Arsenobenzene-with T r i f luoroiodomethane:-Synthesis of Iodophenyltrifluoromethylarsine . 12 (a) Reaction of Iodophenyltrifluoromethylarsine ~ with S i l v e r Chloride 13 (b.) Reaction of Iodophenyltrif luoromethylarsine with Iodomethane i n the Presence of Mercury 13 (c) Hydrolysis 14 (d) Reaction.of Chlorophenyltrifluoromethylarsine with Bis ( t r i f luorome thyl.) arsine 14 (e) Reaction of the Cream Coloured Solid with Hydrogen Chloride 15 ( i i ) Reaction of p-N.itroarsenobenzene with T r i f l u o r o -iodomethane. 15 (;iii) Reaction of Paraaminoarsenobenzene with T r i f l u o r o -iodomethane 15 Section D: Miscellaneous Arsine Reactions 16 ( i ) Reaction of Iododimethylarsine with I o d o t r i f l u o r o -ethylene i n the Presence of Mercury , 16 ( i i ) Reaction of Iododimethylarsine with Hexaf luoro -2 : - . butyne i n the Presence of Mercury 17 ( i i i ) Reaction of T'rime th y l arsine with Bromotr i f luoro-ethylene " 17 Section E;. Some Reactions of DIphosphine and D.itin Cpds.. 17 ( i ) Reaction of Tetrakis(trifluoromethyl)diphosphine with Hexafluoro-2-butyne 17 - i v -TABLE OF CONTENTS (Cont'd) Page ( i i ) Reaction of Hexaphenylditin with Hexafluoro-2-butyne 18 ( i i i ) Reaction of Hexabutyl.ditin with Hexafluoro-2-butyne 18 (iv) Reaction of Tetrakis(trifluoromethyl)diphosphine with Bromotrifluoroethylene . . 1 9 RESULTS AND DISCUSSIONS 20 Reactions of Diarsines with Olefins 20 Reactions of Diarsines with Bis( trifluoromethyl.)ace1ylene 23 Reactions of Arsenobenzenes and Iodotrifluoromethane and Related Reactions 25 Some Miscellaneous Reactions of Iododimethylarsine and Trimethylarsine 29 Some Miscellaneous Reactions of Diphosphines and Di-Tin Compounds 29 Dime thylperfluorovinylarsine 31 BIBLIOGRAPHY 33 ACKNOWLEDGEMENT I express my sincere thanks and gratefulness to Dr. W. R„ Cullen f o r his constant guidance,: assistance and encouragement throughout the experimental work and constructive c r i t i c i s m of th i s manuscript., I also wish to thank Mrs. M. Zell,, Mrs. E . Brion and. Mrs.. A. Aldridge f o r t h e i r help i n the spectroscopic and anal y t i c a l works, and to my colleagues i n the laboratory f o r . t h e i r helpful cooperation. Lastly I wish to express my thanks and appreciation to Dr. C. A. McDowell f o r offering me a teaching assistantship f o r the entire period of studentship i n t h i s university. -1-IN'ffiODUCTION Recently i t has been reported that the a l k y l diphosphines and perfluoroalkyl diphosphines undergo addition reactions with ethylene,, tetrafluoroethylene and acetylene, to give mainly 1:1 addition products,. Thus 1,'2-bis.Cdiethylphosphino)ethane, CGgHg)2?~ CHp-CHg-PCCgKg) g..,. (1), was made by the reaction of t e t r a e t h y l d i — phosphine and ethylene. Tetramethyldiphosphine was reported to react with ethylene at 300° to give 1,2—bis(dimethylphosphino)-ethane (2). Similar reactions of te.trakis(trifluoromethyl)diphos— phine with ethylene, tetrafluoroethylene and a cetylene (3), have been studied. The ease of formation of adducts i s reported to be i n the following order, C0E^>G^^_. With ethylene and, t e t r a k i s ( t r i -fluoromethyl)diphosphine, the reaction goes at room temperature.,, whereas with tetr a f luoroethylene reaction occurs at 165°.. The reaction, of tetrakis.( t r i f luorome thyl.) diphosphine with acetylene goes at 100° giving a 1:1 trans adduct. Krespan has recently shown (4) that hexafluoro-2-butyne reacts with elemental phosph-orus and sulphur to give products containing MC(CFQ)=C(CF0)M. units ClvT- = P or S). These reactions, are formally related to those described above. Cleavage reactions of As-As (5), P-P (5,6,7) and Sn—Sn (8,9) bonded compounds with perfluoroalkyl iodides are known i n which the weak IvT—IvI bond i s cleaved to give perf luoroalkyl derivatives of metal along with the corresponding iodide, f o r example: (CH3)2As-As; (CRg) 2 + CFgl > (CRg)gAsCFg + (CH^gAsI Tetraphenylcyclotetraphosphine and CF 0I react to produce C„HJ?(CF0)I, o b o o CgHgP(.CFg.)g and CgH^PIg ana the mechanism i s believed to be free r a d i c a l mechanism.. + ° 6 H 5 P I 2 N H C 6H 5--P-PC^| 5 C 6 H 5 P ° 2 C 6H 5P(CF 3)I C 6H 5P(GF 3) 2 + C 6H 5PI 2 In the present work the addition reactions of diarsines with ethylene, tet r a f luoroethylene,, CF2=CFX. (X = CI, Br, I) and hexa-fl u o r o - 2 —butyne have been studied. Preliminary investigations, have also been made of the reactions of bromotrifluoroethylene and hexafluoro-2-butyne, with compounds containing P-P and Sn—Sn bonds. The reactions of* arsenobenzenes with i o d o t r i f luoromethane have been investigated, and attempts have also been made to pre-pare perfluorovinyl derivatives of arsenic using reactions anal-ogous to those which have been successful f o r the preparation of perfluoroalkyl arsines. / -3-EXPERIMENTAL Since most of the compounds used.as st a r t i n g materials i n these investigations were reasonably v o l a t i l e and In most cases unstable In a i r and moisture, i t was necessary to use conventional high vacuum techniques f o r t h e i r manipulations. A l l reactions were carried out. by bringing the reactants t o -gether i n previously evacuated pyrex gla.ss reaction tubes, which were subsequently sealed and subjected to. desired conditions.. V o l a t i l e products were p u r i f i e d by trap-to-trap d i s t i l l a t i o n s using suitable low temperature baths. Hon-volatile a i r stable products were d i s t i l l e d - i n vacuo or at constant pressure i n an atmosphere of nitrogen. Whereever possible., vapour chromatogra-phic- techniques, using an Aerograph V.P.C.. instrument with a d i -nonyl phthalate column was used f o r the separation of v o l a t i l e f r a c t i o n s . Molecular weight determinations of v o l a t i l e products were made by Regnault's method.. Infrared Spectra::- Infrared examination has been made use of throughout the present work., f o r i d e n t i f i c a t i o n s of known com-pounds, f o r checking purity and f o r the determination of constit-ution of new compounds. Most of the infrared spectra were recorded on. a Perkin-Eliner Model 21, double beam instrument f i t t e d with sodium chloride optics.. However,, the double beam "Infracord"' made by the same people was found to be extremely helpful f o r quick examinations. The infrared spectra of solids were run as KBr Pellets,, l i q u i d s as f i l m between two sodium, chloride discs, and gases i n a suitable gas c e l l with sodium chloride windows,•which could be evacuated and f i l l e d with gas to the desired pressure. Microanalyses of most of the products are done by Dr. A l f r e d _4-Bernhardt, Max Planck I n s t i t u t , Mulheim (Ruhr), Germany and f o r some products by Mrs. A. Aldridge, microanalyst, Dept. of Chemistry, University of B r i t i s h . Columbia. SECTION A Reactions of Tetramethyldiarsine (Cacodyl) and T e t r a k i s ( t r i f l u o r -ome thyl)diarsine (Perfluorocacodyl) with Olefins and Hexafluoro-. 2-butyne  Preparation of Tetramethyldiarsine Tetramethyldiarsine (from here onwards cacodyl) was prepared by reducing dimethylarsinic acid with hypophosphorous acid (10) i n an inert atmosphere.. The crude product was dried over fused calcium chloride and d i s t i l l e d i n a nitrogen atmosphere.. The f r a c -t i o n d i s t i l l i n g at 43-44° (11 mm.)-was/collected, ( L i t . value 43.8-44.3°, 11 mm.)* In other preparations, the diarsine d i s t i l l e d at 76-77° (50 mm.) (i ) Reaction of Cacodyl with Bromotrifluoroethylene:- Synthesis  of 2-Bromo-1,2-bis(dimethylarsino)—1,1,2—trifluoroethane Cacodyl (4.0 g.) and bromotrifluoroethylene (16.5 g.) were l e f t f o r 7 days at 20°. Qualitative investigation showed that although some reaction had occurred, considerable amounts of cac-odyl were s t i l l present. The reactants were then heated at 50° f o r 5 days. The v o l a t i l e material was taken, to the vacuum, system and about 4.3 g„ of a pale yellow i n v o l a t i l e , a i r stable product was l e f t - i n the tube., The i n v o l a t i l e product d i s t i l l e d at 65° (10~^ mm.) and microanalysis of the compound confirmed I t to be 2-bromo—1,2—  bis(dmethylarsino)-l„l,2-trifluoroethane. Found: C,. 21 .,0; H, 3.,47; As, 40.3; Br, 18.7; F, 16.9 %. Calc. f o r CgH-^ASgBrFg: C, 19.4; H, 3.24; As, 40.4; Br, 21.6; F, 15.4 %. The infrared spectrum of the new compound showed the following absorption bands, (Liquid f i l m ) : 2985m, 2905m, 2800w, 2330w,, 1723s, 1705a, 1420s, -5-1290m, 1265m, 1152m, 1110m, 1067s, 1045s, 1015s, 985m,, 904s, 850s,, 825in, 792s, 682s.cm"1. Trap-to-trap d i s t i l l a t i o n of the. v o l a t i l e f r a c t i o n gave 13.6 g. of unreacted bromotrifluoroethylene,, 0..4 g.. of 1,2-dibromohexafluorocyclobutane, i d e n t i f i e d by i t s infrared spectrum, and 0.2 g. of an unidentified f r a c t i o n (M,, 163), (which on hydrolysis by 10% aqueous sodium hydroxide solution at 100° gave no trifluoroethylene). The infrared spectrum of t h i s f r a c t i o n showed bands at (vapour, main bands only): 3.38m, 3.46m, 5.35m, 5.76m, 7*2m, 7.8s, 8.15s, 8.45s, 8.9s, 9.2s, 9.,9s, 10.3m,, 11.2m,, II.,8m . A further f r a c t i o n (1.7 g.) was also obtained, which was separated by V.P.C. using a dinonyl phthalate column at 135°,. into three main components; namely, bromodimethylarsine (0.4 g.), i d e n t i f i e d by i t s infrared spectrum, and by comparison of i t s retention time with that of a known sample;; fluorodimethylarsine (0.2 go), i d e n t i f i e d by i t s molecular weight of 121 (calc. M, 124) and by i t s infrared spectrum (qualitative analysis showed consid-erable amounts of f l u o r i n e i n th i s f r a c t i o n ) , and an. unidentified f r a c t i o n (0.6 g.) which attacked mercury and on hydrolysis (10% aqueous sodium hydroxide at 100°) gave only a trace of t r i f l u o r -oethylene. The main bands i n the infrared spectrum of t h i s f r a c -t i o n appeared at (vapour): 3*25w, 3.35w, 5.70s, 7.1m, 7.25m, 7.,95m, 8.25s,,, 8.6&, 11.05m, 11.6w, 12..0m, I.3.65ni^ • An ethyl alcohol solution of the adduct reacted with an ethanolic solution of mercuric chloride to give a white precip-i t a t e , which was insoluble i n b o i l i n g ethanol. An infrared spect-rum of the s o l i d showed the absence of any C-F groups, ( i i ) Reaction of Cacodyl with Chlorotrifluoroethylene Chloro t r i f luoroethylene (3.9 g.,) and cacodyl (1.4 g.) reacted on u l t r a v i o l e t i r r a d i a t i o n f o r 24 hours. The v o l a t i l e material from the reaction tube was taken over to the vacuum system and an i n v o l a t i l e product (2.9 g.) remained i n the tube. By trap-to-trap d i s t i l l a t i o n of the v o l a t i l e f r a c t i o n , unreacted c h l o r o t r i -fluoroethylene (2.0g.) was recovered and trimethylarsine (0.4 g.) id e n t i f i e d by i t s infrared spectrum and molecular weight (found* M, 118; calc.: M„ 120) was also obtained. The i n v o l a t i l e product was d i s t i l l e d i n vacuo; the frac t i o n s b o i l i n g at 52-54° (10~ 3 mm.) and 56-58° (10~ 3 mm.) were collected. A constant b o i l i n g point could not be obtained and the product was not very stable i n a i r . The infrared spectrB . of these f r a c -tions were very sim i l a r and showed the following absorption hands ( l i q u i d film):, 3000s,, 2905s, 2430m,. 2330w}l 1730w,, 1662m, 1412m,, 1370w,. 1260m,; 1200m, 1142s,, 1115s, 1105s,. 900m, 85Cm,; 785s, 750m, 665w cm""'". Microanalysis of the. product gave the following r e s u l t s : Found: C„ 23.71; E, 2.48;; As, 25.02;; F, 33.25; CI,, 15.83 %. Calc. f o r C 5H 1 2As. 2ClF 3:. C, 22.04;; H, 3.68;? As, 46.0;. F, 17.5;; Cl„ 11.5 %. ( i i i ) Reaction of Cacodyl with Tetrafluoroethylene Tetraf luoroethylene was prepared by thermal decomposition of Teflon, shavings i n vacuo (11.) and p u r i f i e d by trap-to-trap d i s t -i l l a t i o n . . Cacodyl (1.5 g.) and tetrafluoroethylene (2..9 g.) did not. react when the diarsine was exposed to the o l e f i n at 20°. The mixture was subjected to u l t r a v i o l e t i r r a d i a t i o n f o r 24 hours, and the tube was opened to the vacuum system. Trap-to-trap d i s t i l -l a t i o n of the v o l a t i l e f r a c t i o n gave unreacted tetrafluoroethylene (0.4. g.) and trimethylarsine (0.063 g.), i d e n t i f i e d by i t s i n f r a -red spectrum. The i n v o l a t i l e product (4.3 g.) i n the tube was found to be a i r stable and d i s t i l l e d i n vacuo between 110-125°. Attempts to get a constant b o i l i n g f r a c t i o n f a i l e d . Elemental analysis of the middle f r a c t i o n (b.p. 120°, 10~ 3 mm.) showed i t to be probably a 1:4 addition product of cacodyl and tetrafluoroeth-ylene,., (CH 3) 2Asr-CCF 2CI 1 2) 4-As.(CH 3) 2. Found: C, 23.2;, H, 1.8; As, 22.?;' F, 51.7 %. Gale, f o r G 1 2H 1 2As gF 1 6:; C, 23.6; H, 1.97; As, 24.6; F, 49.9' %. Two other cuts were taken and these analyzed f o r G and H as follows: F i r s t cut,; b.p. 11.0-120° (10~ 3 mm..,), found: C, 23.5; H, 2.38 %, and second cut, b.p.. 120-125° (10~3mm.), found: C, 22.5; H, 1.6 %. The infrared spectra of the three anal-yzed fractions were very s i m i l a r . The spectrum of the supposed 1:4 adduct showed the following absorption bands ( l i q u i d film.): 3.4w,, 3.5w, 7..1m, 8.0m, 8.32s, 8.62s, 8.7s, 8.8s,, 9.12s,; 11.05m, ll.,72m, I2..6w, 12.9m, 13.6m, 14.lw,, 14.4m, 1 4 . 8 S o ^ . (Iv) Reaction of Cacodyl with Iodotrifluoroethylene Cacodyl (1.7 g„) and Iodotrifluaroethylene (10.0 g.) i n t e r -acted at .20° f o r 7 days.- Some yellow s o l i d had formed. After the v o l a t i l e material was taken out to the vacuum system., a colourless.-i n v o l a t i l e l i q u i d was l e f t i n the.tube. Trap-to-trap d i s t i l l a t i o n of the. v o l a t i l e material gave: iodotrifluoroethylene (8.9 g.), a v o l a t i l e unidentified yellow c r y s t a l l i n e s o l i d , bromodimethyl-a rsine and dimethylperfluorovinylarsine. A l l known.compounds were i d e n t i f i e d by t h e i r infrared spectra. The i n v o l a t i l e product was found to be very unstable i n a i r and so could not be d i s t i l l e d . Analysis f o r C and H. showed the following r e s u l t ; found: G, 24.8; H, 4.85 Gale, f o r C H As F I ' 6 12 2 3 C,., 17.2; H, 2.87 %. The infrared spectrum., however, was. si m i l a r t o those of the addu.cts obtained from si m i l a r reactions,, and the following absorption bands were observed, ( l i q u i d f i l m ) : 3000m, 2920m,; 2720w, broad unresolved band (2500-2200)w, broad unresolved - 8 -band (1030-1005) s,, 960m,; 900s, 845s, 805m, 675w cm"1. (v) Reaction of Cacodyl with Ethylene Cacodyl (3.0 g.) and 0.2 moles of ethylene did not react at 20° fo r three months. (vi) Reaction of Perfluorocacodyl with Bromotrifluoroethylene. M e t a l l i c arsenic was heated with iodotrifluoromethane at 220°. Trap—to-trap d i s t i l l a t i o n of v o l a t i l e products gave iodo-bis ( t r i f luorome thyl) arsine.. Ferfluorocacodyl was obtained by shaking Iodobis(trifluoromethyl)arsine with excess of mercury. Perfluorocacodyl (1.53 g.) and bromotrifluoroethylene (4.0 g.) were l e f t at 120° f o r 7 days. Aft e r taking the v o l a t i l e f r a c t i o n of the tube into the vacuum system, some i n v o l a t i l e pale yellow glue remained behind i n the tube. The infrared spectrum of the glue showed the following main bands' (smear): 3.0w,. 3.45w,, 4.4w,, 5.,55m, 5.,7w, 7.35m, 7.,65m., broad unresolved band (8.0-9.0)s,, 1.0 .,8w AJ * Trap-to-trap d i s t i l l a t i o n of the v o l a t i l e content gave 0.8 g. of unreacted bromotrifluoroethylene, and 0.19 g. of t r i s ( t r i f l u o r -ome thyl) arsine.. A t h i r d f r a c t i o n (2.35 g.,) was also obtained which wa s shaken with mercury at 20° f o r 2 days; the v o l a t i l e material recovered weighed 2.05 g. Trap-to—trap d i s t i l l a t i o n of th i s f r a c t i o n Isolated 1,2-dIbromohexafluorocyclobutane, i d e n t i f i e d by i t s infrared"spectrum and molecular weight (Found: . M, 320; C a l c : M, 324).. A. second f r a c t i o n (0.928 g.) was further sep-arated Into three more components by V.P..C at 95°.. The frac t i o n s were i d e n t i f i e d as follows: Component I : - 0.273 g. of a. substance (M,, 280) which hydrolyzed (20% aqueous NaOH at 105°) to give a mixture of fluoroform and t r i f luoroethylene (M, 72.5),, i d e n t i f i e d by i t s infrared spectrum. -9-The infrared spectrum, of t h i s component showed the following absorption bands (vapour): 3.7w, 3.85w, 4.25w,, 4.45w 4.5m, 4„9w, 5..5w, 5.,65m, 5.8s, 7.12w, 7.35m, 7.55s,, 7.9m, 8.3s, 8.5s, 8.65s, 8.9s, 9.0s, 9.7s, lO.ISw,. 10.45w, 13.6s^< On the basis of these results the substance probably was mainly b i s ('tr i f luorome thy 1 ) -perfluorovinylarsine (C^AsFg requires: M,, 294). Component I I : - This f r a c t i o n (0.242 g.) was i d e n t i f i e d to be perfluorocacodyl by i t s infrared spectrum. Component I I I : - (0.566 g.) was i d e n t i f i e d to be 1,2-dibromo-hexafluorocyclobutane by i t s infrared, spectrum and molecular weight, (Found: M, 320; C a l c : M, 324). SECTION B ,. Reactions of Diarsines with Hexafluoro-2-butyne CD Reaction of Cacodyl with Hexaf l u or o—2-butyne Cacodyl.(5.0 g.) and hexafluoro-2-butyne (7.5 g.) reacted instanta neously at. 20° to give a reddish brown l i q u i d product. The tube was l e f t at•20° f o r 2 weeks and then unreacted hexafluoro-2-butyne (4.3 g.) was recovered. No other v o l a t i l e f r a c t i o n found on. trap-to-trap d i s t i l l a t i o n . , The i n v o l a t i l e a i r stable product which was l e f t i n the reaction tube d i s t i l l e d at 42 (10~ mm.). Analysis showed i t to be 1,2-bis(dImethylarsino)-l < 2-bis( trif'luorome thyl) ethylene. Found: C„ 26.5;; H, 2.,9; As, 38.0;; F, 32.7 %. Calc. f o r CgB^gA.SgFg: C, 25.8; H, 3.22; As, 40.3; F, 30.6 %. Infrared examinations of the new compoun(i showed the following absorption bands ( l i q u i d f i l m ) : 2985m, 2915m, 2820w, 2312w, 1570m,, 1429m, 1422m, 1417m,; 1300m,, 1230s, 1150s,, 1135s,; 897m, 867m, 852m, 800w, 710w, 680w, 652w cm"1.. Hydrolysis;,- The adduct (0.283 g.) was subjected to hydrolysis -10-with 15% aqueous sodium hydroxide solution at 110° f o r 5 days. A small amount (0.019 g.) of trans-1,2-b i s ( t r i f luorome thyl) ethylene was produced. The o l e f i n was i d e n t i f i e d by i t s infrared spectrum (12). Mercuric Chloride Complex:- On mixing ethanolic solutions of the new compound and mercuric chloride, a cream white precipitate was obtained. The precipitate was c r y s t a l l i z e d from b o i l i n g ethanol, washed with ethanol and dried i n vacuum. Infrared spectrum of'the complex was examined and the following absorption bands were obser-ved (KBr p e l l e t ) : broad band unresolved (36Q0-3300)m, 3000w, 2920w, 2320w, 1412m, 1230s, 1177s,. 1142s, 925m, 885m, 870m, 654m cm""1., Elemental analysis of the complex suggested i t to be 1:2: adduct of l,,2-bis(dimethylarsino)-l, 2 - b i s ( t r i f luorome thyl) ethylene and mercuric chloride; found: C,.. 11.54; H, 1.29;: As, 12.67;; CI, 14,87; F, 10.73; Hg, 38.1 Calc. f o r C 8H 1 2As 2Cl 4F 6Hg 2: C, 10.5; H, ; 1.31; As, 16.4;. CI, 15.5; F, 12.2; Hg„ 43.8 Thermal S t a b i l i t y Study:- l, ;2-bis(dimethylarsino)-l,2-bis(tri-fluoromethyl)ethylene (0.457 g.) was sealed i n a tube and l e f t at 150° f o r 3 days. The compound was- found to have undergone p a r t i a l decomposition., A black coating was formed on the wall of the tube, some v o l a t i l e material was obtained i n the vacuum system, but no non-condensable gas was formed. The black mass could not be i d e n t i f i e d from i t s X-ray powder photograph. The v o l a t i l e mat-erial.-, was separated into three unidentified components by trap-to-trap d i s t i l l a t i o n using -96°, -130° and -196° baths. The infrared spectrum of a l l the three fractions were examined; they showed the following absorption bands: -96° bath f r a c t i o n (vapour), found: 2980w, 2900w, 2600w, 2550w, 1782m, 1660m, 1415m, 1365m, 1305s, 1275s, 1262s, 1242s, 1217s, 1192s, 1175s, 1117m, 1075w, 1047w, I, 025s., 980w, 892w, 715m cm"1.. -11--130° bath f r a c t i o n (vapour), found: 2975w, 1405w, l'352m}i 1277m, 1269s, 1260m, 11.60w, 950s. (broad),, 825s,, 817s., 715w cm"1.. -196° bath f r a c t i o n (vapour) found: 2300m,, 1370m, 1355m, 1282m, 1275m, 1227m, 1194m., 1025s, 862w, 832m, 755w, 717w cm"1., ( i i ) Reaction of Perfluorocacodyl with Hexafluoro-2-butyne Ferfluorocacodyl (1.53 g..) and hexafluoro-2-butyne (4.9 g.) were,kept at 100° f o r 7 days.. No reaction was found to have occurred.., The reactan.ts were next, l e f t at 150° f o r 10 days. Trap-to-trap d i s t i l l a t i o n of the v o l a t i l e material gave two f r a c -tions. The identity of the two fractions were confirmed to be. the star t i n g materials by infrared examinations. ( i i i ) Reaction of Arsenobenzene with Hexafluoro-2—butyne Arsenobenzene was prepared by reducing ethanolIc solution of phenylarsonic acid with hypophosphorous acid (13),. i n an atmo-sphere of nitrogen. The crude product was washed with absolute ethanol and p u r i f i e d by washing with chlorobenzene at 20°.. The pure product was vacuum dried and used f o r reaction as quickly as possible. Arsenobenzene (.11.0' g.) and hexafluoro-2-butyne. (12.7 g.) were l e f t at 20° f o r 3 days. .No reaction occurred, so the tube was heated to 115° f o r 24 hours. Trap—to-trap d i s t i l l a t i o n of the v o l a t i l e material gave unreacted butyne (.8.5 g.) and a second f r a c t i o n (0.3 g.) of molecular weight 241.2. This was further separated Into two major components by vT.P.C. at 132.5°* Component I : - Infrared spectrum was examined and the following main absorption bands were observed (vapour):: 5.8s,. 7.2m, 7.3m, 7.5m„ 7.72s, 7.8m., 8..Cm., 8.32m, 8.45m, 8.6s, 9.1m, 9.32w, 9.52w, 10.1w, 10.2w, 10.8s, 11.0m, 12.3m, 1 3 . l m ^ . Component I I : - This f r a c t i o n analyzed to be a fluorocarbon. Found: -12-C, 43.93; K, 3.61; F, 52.25 %; calc. f o r C 4H 5F g: C, 43.6; H,, 4.55;" F„ 51.8 %. Infrared spectrum of t h i s f r a c t i o n was also examined and found were the following main absorption peaks (vapour ) : 3.32w, 3.45w, 3.5w, 5.9'Sw, 7.22m, 7..6m, 7.78s, 7.88s, 8.52s, 8.78s, 9.3w, 10.3w, 10.98V!yu -The s o l i d l e f t i n the reaction, tube was extracted with ether. The yellow ether extract on evaporation gave pale yellow wet cry-stals (m.p. 85°), which on further c r y s t a l l i z a t i o n from ether precipitated out benzenearsonic acid. The acid was i d e n t i f i e d by i t s X-ray powder photograph and infrared spectrum. On evaporation of the ether solution,, a yellow glue was obtained. Analysis, of the pale yellow c r y s t a l s (m.p. 85°) gave the following r e s u l t . Found: C,; 28.58;; E, 0.00;; As, 0.28;, F, 65.07 %. The infrared spectrum of the glue was examined and the following absorption bands were ob-served (smear): 3.35m, 6.25m, 6.4m, 6.8m, 7.02m, 7.35w, 7.55m,, • 7.7m, 8.1s, 8.7s, 9.3m, 9.8m, 10.05m., 10.15w,, 1.0.3w, 10.75m, 11.5w, 11.75w, 13.6s, 14.55^64 . The analysis of the glue showed the pres-ence of hydrogen. Found: C, 38.36;, H, 2.87 %. SECTION G Reactions of Arsenobenzenes with Trifluoroiodome°thane (i ) Reaction, of Arsenobenzene with T r i f l u or oiodome thane:- Syn- thesis of Iodophenyltrifluoromethylarsine Arsenobenzene was prepared as described i n the preceding section. Arsenobenzene (1.0.,0 g..) and trifluoroiodomethane (18.0 g.) did not react at 20° (3 days). However, reaction occurred at 115° (24 hours) giving a dark brown l i q u i d product. By trap-to-trap d i s t i l l a t i o n of the v o l a t i l e material i n the. vacuum, system, un-reacted trifluoroiodomethane (5.4 g.) was. recovered and a trace of -13-phenylbis(trifluoromethyl)arsine was isolated. The i n v o l a t i l e a i r stable product was d i s t i l l e d at 65 mm.. In an atmosphere of nitrogen and the following two fractions were obtained. Fraction I, b.p. 88" (65 mm..), which was i d e n t i f i e d to be phenyl-bis ( t r i f luorome thyl) arsine, by i t s infrared spectrum.. Fraction I I , b.p. 158° (65 mm.) was the new product, iodophenyl- t r i f luoromethylarsine .. Anal, found: G, 23..91;; H., 154 %., Calc. f o r C'7H5AsF3I: C, 24.15; H, 1.44 %. The infrared spectrum of the compound showed the following absorption bands ( l i q u i d f i l m ) : 3075m, 2230vw, I980vw,, 1892vw, 1870vw, 1827vw,, 1800vw, 1747'vw, !737w, 1717vw, 1702vw, 1.685vw, 1670vw, 1655vw,, 1637w, 1625vw, I.6Q5vw, 1597vw, 1575w, 1547vw, 1530vw, 1510vw, 1482m, 1435m, 1330m, 1302w,, 1252m, 1185m,, broa d unresolved band peak at l l l O v s , I072s,,: 1020m, 997m,; 9l2vw, 842vw,, 735s, 725m, 687s, 66.8m cm"1. (a) Reaction of Iodophenyltrif luoromethylarsine with S i l v e r Chloride The new arsine (3.4 g.) and freshly prepared, powdered and dried s i l v e r chloride were shaken f o r 2 days at 20°., A colourless l i q u i d , chlorophenyltrifluoromethylarsine„ was produced which was d i s t i l l e d at 118° (65 mm..) i n an atmosphere of nitrogen. Anal, found: C, 33.01; H, 1.76; As, 28.9; CI, 13.6 %. Calc. f o r C 7H 5AsClF 3: C, 32.7;;H., 1.93; As, 29.2; CI, 13.8%. The i n f r a -red spectrum s howed the following absorption, bands ( l i q u i d f i l m ) : 3.3w, 5..75w, 6.35w, 6.75m, 6.98m, 7.3w„ 7.52w, 7.68w, S.Ow, 8.45w, 8.75vs„ 8.95vs, 9.28m, 9.38m, 9.75m, 10.0m, 13.52s, 13.72m, 14.483^. (b) Reaction of Iodophenyltrif luoromethylarsine with Iodome.th- ane i n the Presence of Mercury Iodophenyltrifluoromethylarsine (6.2 g.), lodomethane (13.4 g.) and mercury (90 g.) were shaken f o r 2 weeks at 20°. Trap-to-trap d i s t i l l a t i o n of the v o l a t i l e material gave only one f r a c t i o n , -14-i d e n t i f l e d to be iodomethane (13.3 g.). The "white s o l i d which had formed i n the reaction was extracted with benzene. The benzene solution on evaporation gave pale yellow cr y s t a l s , which were r*e c r y s t a l l i z e d from benzene. • Further attempts i n re c r y s t a l l i z i n g resulted i n the p r e c i p i t a t i o n of benzenearsonic acid,, which was Identified by i t s infrared spectrum. The yellow mother l i q u o r on evaporation gave a yellow glue, the infrared spectrum of which showed the following absorption bands (smear): 3.35w» 4.3w, 4..48W,, 6„4w, 6.8m,; 7.0m, 7.6w, 7.7w, 8.0w, 8.7vs, 9.Ova, 9.4m, 9.8w, 10.05m,, 10.9m,, 12.9m, 13.55s, 13.85w, I4.,5ny4 . (c) Hydrolysis . Ethanolic solution of iodophenyltrifluoromethylarsine was hydrolyzed with excess aqueous sodium hydroxide ('2M).. An o i l was, f i r s t produced, which l a t e r went into solution and addition of a solution of saturated ammonium chloride produced a white precip-i t a t e . The precipitate was washed and dried and i d e n t i f i e d to be phenylarsenious oxide by i t s infrared spectrum and melting point found 140° ( l i t . value 141°). (d) Reaction of Chi orophenyl.tr i f luoromethylarsine with B i s ( t r i - f l u or ome thy 3)ar s ine '. The chloroarsine (0.7 g.) and 0.812 g. of bis(trifluorometh-y l ) arsine were l e f t at 100° f o r 7 days. The tube was opened to the vacuum sys tern. After taking the v o l a t i l e material into the vacuum system, a cream coloured s o l i d was l e f t behind i n the tube. Trap—to—trap d i s t i l l a t i o n of the v o l a t i l e material gave the following f r a c t i o n s : hydrogen chloride (0.043 g.), i d e n t i f i e d by Its molecular weight of 36.6 (calc. M, 36.5); bis(trifluorometh-y l ) arsine (0.466 g.); a f r a c t i o n which contained t r i s ( t r i f l u o r o -methyl ) arsine,, perf luorocacodyl and possibly chl or obis ( t r i f luoro-me thyl) arsine; and chlorophenyltrifluoromethylarsine (0.14 g.)« - 1 5 -A1I the fractions were of known infrared spectrum. The cream coloured s o l i d i n the tube was found to be unstable i n a i r and highly hygroscopic' Anal, found: C, 36.47;: H, 2.33 %• The infrared spectrum of the compound was examined and the f o l l o w -ing absorption bands were observed (smear): 3.35m, 4.3w, 4.45w, 5.18vw, 5.,4vw, 5„6vw, 5..75vw, 6.1w, 6.4w, 6.8m, 7'.,02m, 7.55w,. 7.,72w, 7.,95w, 8..05w, 8.5m,, 8.85s, 9.1s, 9.4s, 9.8m, 10.05m,, 10.9m, 11.8w, 12.8m, 13.6s, 13.85m, 14.45s, 14.7w, 1 4 . 9 w . . The end product of the decomposition of the s o l i d i n a i r was benzenearsonic acid ( i d e n t i f i e d by i t s X-ray powder photograph), (e). Reaction of the Cream Coloured Solid with Hydrogen Chloride The cream s o l i d was prepared as above in. a sealed tube with a constriction i n the neck.. The v o l a t i l e material was taken into the vacuum system and 0.82 g. of hydrogen chloride was condensed into the tube. The tube was then kept at 100° f o r 24 hours. The tube was opened to the vacuum system. Trap-to-trap d i s t i l l a t i o n of v o l a t i l e f ractions gave unreacted hydrogen chloride, b i s ( t r i -fluoromethyl)arsine, chlorophenyltrifluoromethylarsine, a f r a c t i o n which could be phenylbis(trifluoromethyl)arsine and a trace of t r i s ('trif luorome thyl) arsine. A l l were i d e n t i f i e d by means of t h e i r infrared spectra., ( I i ) Reaction of p-Nitroarsenobenzene wit.h Trifluoroiodomethane Paranitroarsenobenzene was prepared (13) by reducing para-nitrobenzenearsonic. acid with hypophosphorous acid at 55—60° In an atmosphere of nitrogen. Paranitroarsenobenzene (15 g.) and 33.7 g. of t r i f l u o r o i o d o -methane were l e f t at 110°, after a few hours the reaction tube exploded. The reaction was repeated with the same r e s u l t . ('Ill) Reaction of Paraaminoarsenobenzene with T r i f luoroiodome thane -16-. Paraamlnoarsenobenzene was prepared (14) by reducing a .solu-t i o n of paraaminobenzenearsonic acid i n 2N sodium carbonate solu-t i o n containing magnesium chloride hexahydrate, with sodium hypo-sulphite i n ice water,, at 55-60° f o r 1% hours. Paraaminoarsenobenzene (1.0 g.) and t r i f luoroiodomethane (.1.5.7: g.) did not react at 20°„ The reaction tube was then kept at 115° f o r 7 days. A dark brown s o l i d was. formed. V o l a t i l e material of the tube was taken, to the vacuum system. Trap—to—trap d i s t i l l a t i o n of the v o l a t i l e f r a c t i o n separated 1.0.2 g. of t r i -fluoroiodomethane and 0.7 g. of a second f r a c t i o n . This second f r a c t i o n was put through V. P. G. at 1.35° and two components, were Isolated. These two components were, i d e n t i f i e d as follows: Component. I;,— Identified, to be o r t h o t r i f luoromethylaniline by i t s infrared spectrum and analysis. Anal, found: C, 53.13; H, 4.19 %. Calc. f o r CgHgFgN:: C',. 52.2; H, 3.73 %. Component I I : — I d e n t i f i e d to be an i l i n e by i t s infrared spectrum and analysis. Anal, found: C, 76.93; H, 7.46 %, Calc. f o r GgH^N: C,, 77.4; H, 7.50 %. The dark brown s o l i d i n the reaction tube was extracted with ether. The yellow ethereal solution on evaporation gave a yellow gum.,, which on the evidence of infrared spectrum, was found to be mainly a mixture of ani l i n e and' o r t h o t r i f luoromethylaniline. SECTION D  Miscellaneous Arsine Reactions (I) Reaction of Iododimethylarsine v/ith Iodotrif luoroethylene i n the Presence, of Mercury Iododimethylarsine (24.2 g.),, 240 g.. of mercury and i o d o t r i -fluoroethylene (66 g.) were shaken f o r 10 days at 20°.. 'By trap-to-trap d i s t i l l a t i o n of the v o l a t i l e material of the tube separated, -17-64.4 g. of iodotrifluoroethylene, i d e n t i f i e d by i t s infrared spec-trum and dimethylperfluorovinylarsine (1..0 g.) of mol. wt. 181 (calc. M,, 186). The arsine was further p u r i f i e d by V. P. C. at 55°. Anal, found: C, 26.0; H, 3.31; As, 40.25;; F, ,30.43 %., Gale, f o r C4HgAaFg:. C, 25.8; H, 3.26; As, 40.40;; F, 30.60 %. The infrared spectrum of the new arsine v/as examined and the f o l -lowing absorption bands were observed (vapour): 3010m, 2920m,, 2825w, 2580w» 1780w,; broad (1740-1725) s, broad (1435-1415 )m, 1300s, 1140s, 1020s,, 897m, 852m, 715m cm"1. Hydrolysis:- The arsine (.0.08.6 g.) v/as subjected to hydrolysis, with 15% aqueous sodium hydroxide solution at 100° (24 hours). Trap-to- trap d i s t i l l a t i o n of the v o l a t i l e f r a c t i o n gave t r i f l u o r o e t h -ylene (0.0099 g.) and unreacted dimethylperfluorovinylarsine. ( i i ) Reaction, of Iododimethylarsine with Hexafluoro—2-butyne i n  the Presence of Mercury Iododimethylarsine (21.0 g.) and hexafluoro-2-butyne (30.0 g.) did not react on shaking f o r 7 days at 20° i n the presence of 217 g. of mercury. ( H i ) Reaction of Tr ime thy l a r sine with Bromotrifluoroethylene Trimethylarsine (0.6 g.) and bromotrifluoroethylene (6.5 g.,) were, kept at 20° f o r 12 months. Trap-to-trap d i s t i l l a t i o n of the v o l a t i l e material recovered 6.4 g. of bromotrifluoroethylene and 0.54 g. of t r imethylarsine. No dimethylperfluorovinylarsine was isolated. A small amount of unidentified brown s o l i d had precip-itated from the reaction mixture. SECTION E. Some Reactions of Diphosphine and D i t i n Compounds (i ) Reaction of Tetrakis(trifluoromethyl)diphosphine with Hexa- f l u o r o-2-butyne Tetrakis(trifluoromethyl)diphosphine (2.9 g.) and hexafluoro--18-2-butyne (7.6 g.) did not react a t 100° (2 days). A cream coloured s o l i d was, however, formed on keeping the reactants at 200° (3 days). Trap-to-trap d i s t i l l a t i o n of the v o l -a t i l e material gave 2.7 g. of the butyne and 1.5 g. of the diphos-phine, i d e n t i f i e d by t h e i r infrared spectra. The s o l i d l e f t i n the tube was extracted with ether. The yellow ethereal solution was separated from an insoluble cream coloured s o l i d and the solution on evaporation gave an' unident-i f i e d yellow glue. The cream coloured s o l i d (m.p. 300°) was found to be insoluble i n organic solvents. Analysis showed the following r e s u l t s . Found: C, 28.66; H, 0.00 %. Infrared spec-trum of the s o l i d showed the following absorption bands (KBr p e l -l e t ) : broad unresolved band (1270-1225) vs,; broad unresolved band (1200-1150)vs, 962w, 877m, 767m, 710m cm"1. ( i i ) Reaction of Hexaphenylditin with Hexafluoro^2-butyne Hexaphenylditin (7.0 g.) and hexaf luoro-2-butyne (11.0 g.) were kept at 200° f o r 18 hours. By trap-to-trap d i s t i l l a t i o n of the v o l a t i l e f r a c t i o n , 10.9 g. of butyne was recovered and the remaining s o l i d l e f t in. the tube was i d e n t i f i e d to be hexaphenyl-d i t i n by i t s infrared spectrum. ( i i i ) Reaction of Hexabutylditln with Hexafluoro-2-butyne Hexabutylditin (8.9 g.) and hexafluoro-2-butyne (10.0 g.) were kept at 75° for 15 days. By trap-to-trap d i s t i l l a t i o n of the v o l a t i l e material, 8.8 g. of butyne was recovered. The non-volatile f r a c t i o n was a mixture of a s o l i d and a l i q u i d . The l i q u i d was Identified to be hexabutylditin by Its infrared spectrum. The white s o l i d was c r y s t a l l i z e d from ethanol. The analysis of the white sol i d (decomp. 180°) showed the following r e s u l t s , found; C, 47.3; H, 8.65; Sn, 31.5; F, 8.37 %. Calc. f o r (C H ) SnF: C, 4 9 3 -19-4.6..5;; H, 8.75; Sn, 38.4; F, 6.15 %. Infrared spectrum of the so l i d , was examined and the following absorption peaks were observed (KBr p e l l e t ) : 2900s, 2840m, 1462m, 1450m, 1412w, 1375m, 1337w, 1330w, 1265m, 1250m, 1225m, 1145s,. 1.075m, 1020%, lOOOw, 960w, 875m, 695m,; 670m cm"1. (iv) Reaction of Tetrakis (trifluoromethyl)diphosphine with Bromo- t r i f l u o r oethyIene Tetrakis(trifluoromethyl)diphosphine (4.0 g.) and bromotri-fluoroethylene (11.8 g.) were kept at 120° f o r 11 days. The tube was opened to the vacuum system and v o l a t i l e material taken into the vacuum system. A yellow glue was l e f t behind i n the tube. Anal, found: G, 15.81: F,,. 36.31; Br, 40.13;, P, 3.41 % and mol. wt. 635. The material was unstable to a i r . Trap-to—trap d i s t i l l a t i o n of the v o l a t i l e f r a c t i o n gave the following: bromotrifluoroethylene (4.3 g.), dibromohexafluorocy-clobutane (3.0 g.), i d e n t i f i e d by i t s infrared spectrum and mol. wt. (found: M, 320.3;, c a l c : H, 324), and a mixture (2.0 g.) of bromobis(trifluoromethyl)phosphine and possibly b i s ( t r i f l u o r o -me thyl) perf luorovinylphosphine. This mixture on .hydrolysis by water' gave fl u o r o f orm and bromide ion i n solution,; but did not produce trifluoroethylene on alkaline hydrolysis at 20°. The mixture was shaken with water (3 months) and trap—to—trap d i s t i l -l a t i o n of the v o l a t i l e material separated a f r a c t i o n which on the evidence of i t s infrared spectrum, could possibly be b i s ( t r i f l u o r -omethyl)perfluorovinylphosphine. The infrared spectrum of th i s f r a c t i o n showed the following main absorption bands (vapour): 4..45m, 4.52m, 5.82s, 7.3m, 7.5s, 8.,3vs, 8.42vs, 8.6vs, 8.9vs, 9:.5s, 9.72m, 11.12m, 13.3s M . -20-RESULTS AND DISCUSSIONS Reactions of Diarsines with Olefins A l k y l and perfluoroalkyl diphosphines undergo addition reactions, with o l e f i n s , perfluoroethylene and acetylene, r e s u l t i n g i n the diphosphino derivatives of the corresponding alkanes and alkene (1,2,3),. e.g.. (CF 3) 2P-P(CF 3) 2 + CH2=CH2 >.(CF 3) 2P-CH 2-CH 2-P(CF 3) 2 . I t has now been found that tetramethyldiarsine undergoes simi l a r reactions with f l u o r i n e containing olefins producing d i -arsino derivatives. Thus tetramethyldiarsine when reacted with bromotrifluoroethylene at 50° (7 days) gives a product,, which analyses to be 2-bromo-l,2-bis(dimethylarsino)-l,l,2-trifluoro-ethane,, as the main product of the reaction, i . e . (CRgJgAs-As (CH 3) 2 + CF2=CFBr —->• (CHg)gAs-CFg-CFBr-As(CHg)2 Small, amounts of bromodime th y l arsine and f luorodimethylarsine are also isolated. The fluorodimethylarsine i s probably formed by elimination from the diarslne adduct. Similar elimination of fluorodimethylarsine has been observed In the reaction of hexa-fluofocyclobutene and tetramethyldiarsine ( i j ) . The reaction path i n t h i s reaction Is believed to be the following: As(CH ) (CH3)2As.-Aa(CH3).2 + CF=CF-CF2-CF2 > |jCH 3) gAs.-pF-CFg-CF^F3 (CH3) gAa-O-^CF-CFg-CFg + FAs.(CHg)2 The diarsino compound, i s a new compound, b.p. 65° (10 3mm.) and. i s f a i r l y stable i n a i r . The compound reacts with mercuric chlor-ide i n ethanolic solution, but the mercuric chloride adduct Is insoluble In and appears, to be unstable to b o i l i n g ethanol, since the insoluble precipitate contains no fluorocarbon groups. -21-Ih the reaction of tetramethyldiarsine and c h l o r o t r i f l u o r o -ethylene under u l t r a v i o l e t I r r a d i a t i o n (24. hours), an i n v o l a t i l e product i s obtained, which d i s t i l l s at 52-54° (10~^mm.).. This b o i l i n g point i s what can be expected f o r a 1:1 adduct, i n view o —3 of, the b o i l i n g point of 6-5 (10 mm.) of the adduct with bromo-trifluoroethylene. However, analysis of t h i s fraction, shows, that the product i s impure. The a n a l y t i c a l figures, suggest that the f r a c t i o n contains 2-chloro-l,2-b.is(.dimethyIarsino)-l,l,2-trifluor-oethane, associated with a telomer of chlorotrifluoroethylene. Calculation f o r a mixture of the 1:1 adduct and c h l o r o t r i f l u o r o -ethylene i n a 1:2.36 r a t i o , assuming analysis of arsenic to be correct, shows the following r e s u l t s : Anal, c a l c f o r mixture of (CH 3) 2As-Cr 2-CFCl-As(CH 3) 2, + 2.36 (CF2=CFC1): C, 21.5; H, 2.0; As, 25.0; F, 32.0; CI, 19.9%. Found: C, 23.71; H, 2.48; As, 25.0; F, 33.25; CI, 15.83%. The other product of the addition reaction i s trimethylarsine, but no fluorodimethylarsine can be detected. The reaction of iodotrifluoroethylene and tetramethyldiarsine at 20° (7 days), gives mainly an i n v o l a t i l e product. However, the product i n t h i s case i s highly hygroscopic, unstable, and fumes i n a i r . Elemental analysis of the product shows higher carbon and hydrogen content than i s expected in. an adduct. I t i s suggested that the i n i t i a l l y formed adduct eliminates fluorocarbon i n a i r and oxidizes to form, the same sort of oxidation products as does tetramethyldiarsine. The infrared spectrum of the product was found to be. very s i m i l a r to the other adducts of t h i s kind.. The other products of the reaction are, iododimethylarsine and dimethyl-perfluorovinylarsine, a new compound. The formation of dimethy1-perfluorovinylarsine can be accounted f o r by the following scheme: CCH 3) 2As-As(CH 3) 2 + CF2=CFI > (CHg )2As-CF=CF + (CHg) Aal -22-Iodotrif luorome thane reacts s i m i l a r l y with the diarsine (5)': (CHg) gAs—As(CHg) 2 +. CFgl > CCRgJgAsCFg + (CRg^AsI Tetrafluoroethylene does not react with tetramethyldiarsine at 20°. But reaction occurs under u l t r a v i o l e t i r r a d i a t i o n f o r 24 hours, giving a product, b.p.. 110-125° (10 ^ mm.). The middle f r a c t i o n of t h i s product, b.p. 115-120° analyses to be the 1:4 addition product of tetramethyldiarsine and tetrafluoroethylene, namely l,8-bis(dimethylarsino)perfluorooctane. The formation, of a 1:4. adduct instead of a 1:1. adduct can be explained by consid-ering the high tendency of polymerization of tetrafluoroethylene under the conditions of the experiment. This r e s u l t indicates that the reaction proceeds by a free r a d i c a l reaction mechanism,, which may be represented as follows:. GF2=CF2) CF 2-CF 2 (CHgOgAs-AsCCHgJg + GF 2-CF 2 > (CHg) gAs.-CFg-CFg + A°s(CHg)2 (CHg^sCFg-CFg + CF 2-CF 2 > (CHg) gAsCFg-CFg-CFg-CFg (CHg)2As,-(CF2)g-CF2 + CF 2-CF 2-—> (CHg) gAs-(CF 2) g-CF2; (CHg) 2Aa(CF 2) 5-CF 2 + CFg-CFg > (CHg) gAs-tCF^ 7-CF 2 (CHg) 2As-(CF 2) 7 CF 2 + As(CHg) 2 > C.CHg) 2As-(CF 2-CF 2) 4-Aa(CHg) 2 A trace of t r imethylarsine i s also obtained as a biproduct of th i s reaction. Tetramethyldiarsine does not react with ethylene at 20° (3 months) to give an addition product. The reaction of tetrakisfrrifluoromethyl)diarsine and bromo-trifluoroethylene at 120° (7 days) does not give: an addition prod-uct, however i t results In extensive polymerization of' the olefin.. The reaction gives a large amount of the dimer of the o l e f i n , namely 1,2-dibromohexafluorocyclobutane., A higher polymer, a -23-yellow glue of unknown constitution and degree of polymerization Is also formed. Other products of the reaction are t r i s ( t r i f l uor-ome thy1)arsine, bromobis(trifluoromethyl)arsine, and a f r a c t i o n , mol. wt. 280. The infrared spectrum of t h i s l a s t f r a c t i o n shows the presence of a double bond. The f r a c t i o n i s hydrolyzed by a l k -a l i to give a mixture of fluoroform and t.r i f luoroethylene. This suggests that t h i s f r a c t i o n i s mostly bis(trifluoromethyl)perfluor-ovinylarsine,, mol. wt. 294. Thus i n general one can conclude that the f l u o r o o l e f i n s form addition compounds with tetramethyldiarsine. A si m i l a r addition reaction has been found i n the case of hexafluoropropene and t e t r a -methyldiarsine (IB): (CHg)gAs-As(CHg)g + CF2=CF-CT3 > (CHg)gAs-CFg-CFtCFgJ-AstCHg)2 The s t a b i l i t y of the adduct i n a i r seems to be miximum when the o l e f i n i s tetrafluoroethylene and minimum when the o l e f i n i s iodo-t r i f luoroethylene. The infrared spectra of a l l the d i a r s i n o f l u o r -ohaloethanes are very s i m i l a r to each other. Reactions of Diarsines with B i s ( t r i f luoromet.byl)acetylene Krespan (4) has recently shown that bis(trifluoromethyl)acet-ylene (hexafluoro-2-butyne) reacts with elemental phosphorus end sulphur to give products containing MC(CFg)=C(CFg)M units (M = P. or S ) . Grant (3) has found that tetrakis(trifluoromethyl)diphos-phine reacts with acetylene to produce trans-1,2-bis(trifluorometh-ylphosphino)ethylene as follows: (CFg ) 2P-P (CFg) 2 +. GHSGH ± (GFg) gP-CH^CH-P ( GFg) 2 ; Thus, i t would be expected that compounds containing As-As bonds would react with acetylenes to give products related to those -24-obtained i n the section above. Hexafluoro-2-butyne has been found to react with tetramethyl-diarsine at 20°,. almost instantaneously, to give an a i r stable product, b.p. 42° (10~3mm.). Analysis of t h i s product indicates, i t to be the 1:1 addition product, 1,2-bis(dimethylarsino)-1,2-bis(trifluoromethyl)ethylene. (CH 3) 2As-As(CH 3) + CF3-C=C-CF3 > (CHg) 2As-:(CFg)C=C(CFg)-As(CHg), Alkaline hydrolysis of the adduct with 15% aqueous sodium hydroxide solution at 110° produces trans-1,2—bis(trifluoromethyl)ethylene. The ethanolic solution of the diarsinoethylene compound and mer-curic chloride react to give a cream white s o l i d , which c r y s t a l -l i z e s from b o i l i n g ethanol. The analysis of t h i s cream coloured adduct suggests i t to be mostly a 1:2 adduct of the l , 2 - b i s ( d i -methylarsino)-!,2-bis(trifluoromethyl)ethylene and mercuric chlor-ide. A els compound would be expected to give a 1:1 complex with mercuric chloride as follows: CEL GHr, \ y/ CF£^.—-As' Gl These results together suggest that.the adduct l , 2 - b i s ( d i — methylarsino)-l,2-bis(trifluoromethyl)ethylene i s mostly a trans compound. Treichel, Pitcher and Stone (Iff) have reported that manganese pentacarbonyl hydride undergoes addition reaction with hexafluoro-2-butyne to give a trans adduct, as follows: CF 3 Mn(C0)5 CF 3-CsC-CF 3 + HMn(C0)5 > ^ C = C ^ H CFg The diarsinoethylenic compound undergoes p a r t i a l decomposition -25-at 150° (3 days), giving v o l a t i l e material and a black s o l i d which does not contain much arsenic metal. On extending t h i s 'type of addition reaction of hexafluoro-2-butyne to other diarsines, i t i s found that t e t r a k i s ( t r i f l u o r o -me thyl)diarsine does not react with the butyne at 150°. Arsenobenzene and hexafluoro-2-butyne gave no addition prod-uct at 100°. A very small amount of v o l a t i l e material i s produced which Includes a fluorocarbon derivative of empirical formula C^HgFg. A pale yellow c r y s t a l l i n e s o l i d , m.p. 85°, soluble i n ether Is also obtained, analysis of which indicates i t to be a polymer of hexafluoro-2-butyne. The ether solution deposits crystals of benzene arsonic acid. T h i s i s probably formed by oxidation of unreacted arsenobenzene (IgO. The acid i s Insoluble i n ether. The yellow c r y s t a l l i n e ether soluble s o l i d l a t e r becomes a yellow glue when attempts are made to r e c r y s t a l l i z e i t from: ether. The formation of the.glue may be due to association of ether molecules i n the c r y s t a l s in. some way. This suggestion gains support from the a n a l y t i c a l figures of the glue, which .show an increase i n carbon content and the presence of hydrogen. Reactions of Arsenobenzenes and Iodotrifluoromethane and Related Reactions As described i n the introduction, the compounds containing weak bonds such as As-As}J P-P and Sn-Sn are readily cleaved when treated with perfluoroalkyliodides. Thus tetraphenyltetracyclo-phosphine Is cleaved by iodotrifluoromethane as follows: HS-I-I-X + C ? 3 X * W ^ s " * C6 HS P< 0 F3 )2 ; + C 6 H 5 P I 2 5 6 6 5 In the present investigations, arsenobenzene has been found -26- 0\ to undergo si m i l a r cleavage reaction with iodotrifluoromethane. The reaction does not occur at 20°; however i t goes smoothly at. 115° (24 hours) or on u l t r a v i o l e t i r r a d i a t i o n , giving r i s e to a i r stable products. The products of the reaction are p h e n y I b i s ( t r i -fluoromethyl)arsine, b..p. 83° (65 mm.),, diiodophenylarsine,, and a pale yellow l i q u i d , b.p.. 158° (65 mm.). The pale yellow l i q u i d analyzed to be iodophenyltrif luoromethylarsine. The reaction is. believed to b e a free r a d i c a l reaction and. the following reaction mechanism i s suggested: 3" hv or <A . . CFoI 1 •CT„. + I G A ?6 H5 !6 5 I n n C.H.-As As „ A S ^Lp.kic- O O I . p W W f T F } H 5C 5-A^A S-C 6H 5 t ^ H 5 = 6 - ^ - t i 0 ^ C^H.-As C„JT -As-CF. 6 5 | 6 5 | 3 , o CH-L + ^ S 1 —»>. l l - L O K f O H i a + W ^ s f e + °6 H5 A S I2 6 5 |0 D O | o o o C 6H 5-Ae C6H5-As-I. C-H^-As. CRHe.-As-CFf5 Iodophenyltrifluoromethylarsine Is a new compound, the eth-anol i c solution of which Is hydroxyzed by 2M aqueous sodium hydrox-ide solution to give phenylarsenious oxide. The new iodoarsine does not couple with iodomethane i n the presence of mercury to give CgHgAs^EgJCHg, instead a cream white s o l i d soluble i n benzene Is produced., The s o l i d on c r y s t a l l i z a t i o n , from benzene gives pale yellow c r y s t a l s . Further p u r i f i c a t i o n results i n the formation of benzenea rsonic acid and evaporation of the benzene solution affords -27-a yellow glue. These results suggest that the pale'yellow s o l i d i s produced by the coupling of two molecules of iodophenyltri-fluoromethylarsine. The r e s u l t i n g diarsine decomposes i n a i r to give benzenearsonic acid. Iodophenyltrifluoromethylarsine reacts with freshly prepared methylarsine. This chloroarsine i s a new compound and i t s form-ation and characterization affords additional confirmation f o r the Identity of the parent iodophenyltrifluoromethylarsine. The new producing mainly a cream coloured s o l i d , hydrogen chloride,, t r i s -Ctrifluoromethyl)arsine and tetrakis(trifluoromethyl)diarsine. The cream coloured s o l i d i s unstable i n a i r and the end product of decomposition i n a i r i s found to be benzenearsonic acid. The elimination of .hydrogen chloride suggests the cream s o l i d to-be a diarsine, analysis of which suggests i t to be a symmetrical 1,2-bis(phenyl)'-1,2-bIs(trifluoromethyl)diarsine, rather than the exp-ected unsymmetrical 1-phenyl-l, 2,2-tris( t r i f luoromethyl)diarsine and the following reaction scheme may be suggested.: C 6H 5As(CF 3)I + Hg + ICCF 3)AsC 6H 5 > C 6H 5(CF 3)As-As(.CF 3)C 6H 5 s i l v e r chloride at 20°,. producing a colourless a i r stable l i q u i d b..p. 118° (65 mm.), which analyzes to be chlorophenyltrifluoro— chl or oars ine reacts with bis( t r i f luoromethyl) arsine at 100° (7 days),, CgH 5As(CF 3)Cl : + HAs(.CF3) 2 + HCl As-As + HCl 'As-H •+ Cl-As \ CF 3 -28-CA /OA CA sCA 6 5 / 6 5 6 5. / 6 5 >s-H + CI-As > As-As. + HG1 C F g ^CFg CFg ^ F g , (CFgJgAsH + CIAs(CFg)g — ( C F g ) g A s - A s ( C F g ) g + HC1 The o r i g i n of t h i s t r i s ( t r i f l u o r o m e t h y l ) a r s i n e i s unknown,, but i t i s suggested that i t may have formed as the r e s u l t of a r e d i s t -r i b u t i o n reaction of a compound containing (CFg)gAs- units (Z§p2'0)'. The infrared spectra of the cream coloured diarsine and that of the pale yellow c r y s t a l l i n e diarsine obtained by coupling of iodo-phenyltrifluoromethylarsine and mercury are i d e n t i c a l . The cream coloured diarsine undergoes cleavage reaction with hydrogen chlor-ide at 100° giving bls(trifluoromethyl)arsine, chlorophenyltri-fluoromethylarsine, a trace of tris(trifluoromethyDarsine, and a f r a c t i o n which may be phenylbis(trifluoromethyl)arsine. These results and t h e i r r e l a t i v e amounts suggest that the s o l i d i s a mixture of symmetrical and unsymmetrical diarsines, the symmet-r i c a l one being the major component. Attempts were also made to react iodotrifluoromethane with substituted arsenobenzenes. Paranitroarsenobenzene reacts with iodotrifluoromethane explosively at 110°. The reaction of para-amlnoarsenobenzene with iodotrifluoromethane at 115° produces, a dark brown s o l i d and two v o l a t i l e l i a u i d s , which analyze to be orthotrifluoromethylaniline and a n i l i n e . The dark brown s o l i d on extraction with ether and evaporation of the ethereal solution gives a yellow glue. On evidence of infrared spectrum, the glue i s found to be mainly a mixture of aniline and o r t h o t r i f l u o r o -methylaniline . The lack of any As-As cleavage reaction i n t h i s case can be attributed to the f a c t that the par.aaminoarsenoben-zene had already decomposed when used f o r the reaction. -29r Some Miscellaneous Reactions of Iododimethylarsine and Trimethylarsine Iddodimethylarsine i s known to react with perfluoroalkyl iodides i n the presence of mercury (5-1) to give perfluoroalkyl derivatives of arsenic, e.g. (CHg) 2AsI + Hg + ICF 3 > (CH 3) 2AsCF 3 + Hglg I t has now been found that iododimethylarsine. reacts s i m i l a r l y with iodotrifluoroethylene i n the presence of mercury to give a v o l a t i l e product of mol. wt. 181, which analyzes to be dimethyl-perfluorovinylarsine. . (CH 3) 2AsI + Hg + ICF=CF2 , ^ (CHg)2AsCF=CF2 + H g l g This i s a new compound, stable i n a i r and can be p u r i f i e d by vapour phase chromatography. I t i s known that trimethylarsine undergoes an exchange reac-t i o n with iodotrifluoromethane giving a perfluoroalkyl derivative of the arsine ( 2 i ) , e.g. CCHgJgAs + CFgl ^ CCHg)2AsCFg + CHgl I t i s found i n the present investigation that trimethylarsine. does not undergo an exchange reaction with, bromotrifluoroethylene at 20°, to give dime thy l p e r f luorovinylar-sine. S i m i l a r l y , iododimethylarsine does not react with hexafluor-o-2-butyne In the presence of mercury to give an addition product. Some Miscellaneous Reactions of Diphosphines and Pi - T i n Compounds Tetrakis(trifluoromethyl)diphosphine i s known to give addition products with acetylene (3), e.g. (CFg)gP-P(CFg) 2 + CHSCH > (CFg)gP-CH^H-P(CFg)g I t has now been found that tetrakis(trifluoromethyl)diphosphine does not give an addition compound with hexafluoro—2—butyne at -30-200° (3 days)., However., t h i s reaction produces an ether soluble yellow glue and a cream coloured amorphous, s o l i d , m.p* ^ 300°, insoluble i n organic solvents, which analysis sugges ts to be a polymer of the butyne. Boston, Sharp and Wilkinson (2-2) have also reported a high polymer of butyne which has the same physical properties as the present polymer. The yellow glue may probably be a polymer containing phosphino units, e.g. (PCTg) n, which can also account f o r the loss of diphosphine i n the reaction. Hexafluoro-2-butyne does not react with hexaphenylditin at 200°. The reaction of hexabutylditin with hexafluoro-2-butyne at 75° (15 days),, d.oes not seem to give an addition compound. An unidentified white s o l i d (dec. 180°), soluble i n ethanol, i s pro-duced. Analysis of t h i s s o l i d shows some resemblance to t r i b u t y l -t i n fluoride,, but the infrared spectra of the unknown and known sample are not i d e n t i c a l . The s o l i d , however, shows strong C-F absorption i n i t s Infrared spectrum, thus accounting f o r the loss of butyne i n the reaction. The reaction of tetrakis(trifluoromethyl)diphosphine and bromotrifluoroethylene at 120°, does not give an addition compound; however,, i t results i n extensive polymerization of the olefin.. As a r e s u l t , the dimer of bromotrifluoroethylene and a yellow glue, which fumes In a i r , possibly due to the presence of some phos-phorus, compound,, are is o l a t e d . The analysis and mol. wt. deter-mination of the glue suggest the p o s s i b i l i t y that i t may be the tetramer of bromotrifluoroethylene. The other products of t h i s reaction are bromobis(trifluoromethyl)pbosphine and a f r a c t i o n which on the evidence of i t s infrared spectrum, i s probably b i s -(trifluoromethyl)perfluorovinylphosphine. These two products are -31-perhaps formed by the cleavage'of the P-P bond of the diphosphine by the bromotrifluoroethylene, e.g.. , . . (CF 3) 2P-P(CF 3) 2 + CF2=CFBr — » (CF^gPBr + (CFg)gPCF^CFg DimethyIperfluofovinylarsine The vapour pressure of dimethylperfluorovinylarsine at var-ious temperatures i s as follows:: t C°C) p (cm.) 21 9.43 27 11.80 31 14.70 34.5 17.25 38 20.05 42 23.73 46. 28.30 51.6 35.45' 56.5 43.00 60.7 50.35 A p l o t of ^ (abs.) against log p i s l i n e a r . The normal b o i l i n g point of dimethylperfluorovinylarsine i s estimated to be 71 °C, by extrapolation. ..The latent heat of vaporization i s c a l -culated to be 8180 cals./mole, and Trouton's constant i s found to be 23.8.. Alkaline hydrolysis of a l l trifluoromethyl derivatives of. arsenic y i e l d fluoroform or a mixture of fluoroform and f l u o r i d e ion (20). (CF 3) 3As ~^-> (CFg)gAsOH + CFgH.2" 0 H > NaHgAsOg + 3 CFgH Investigation of the aqueous alkaline hydrolysis of t r i s ( t r i f l u o r -omethyl) arsine and the mixed methy1trifluoromethyl-, methylphenyl-trifluoromethyl—, and phenyltrifluoromethyl-arsines has shown that the rate increases as the number of t r i f luoromethyl groups, i n c --32-reases and that the alkyltrifluoromethylarsines are more easily hydroxy zed than a r y l t r i f luoromethyla rsines (23,2.4). Recently Kaesz, Stafford and Stone (25) have reported that t r i s ( p e r f l u o r -ovinyl)arsine i s stable to base, although the actual conditions of t h e i r experiment are not reported. However, i n the present i n -vestigation, i t has been found that dimethylperfluorovinylarsine y i e l d s 26%' of the perfluorovinyl group as t r i f luoroethylene when subjected to hydrolysis with 15% aqueous sodium hydroxide at 100° f o r 24 hours. In the present investigation, i t i s also found that a compound which most probably i s bis(trifluoromethyl)perfluoro— vinylarsine y i e l d s a mixture of fluoroform and trifluoroethylene on,alkaline hydrolysis at 105°, and no s t a r t i n g material was r e -covered. Thus the f i n d i n g of the present Investigation i s i n consistence•with the general hydroxytic trend of the perfluoro— alkylderivatlves of arsenic. -33-BIBLIOGRAPHY 1.. C. E. WYMORE. Dissertation abstract,. 17, 1208 (1957). 2. A. B. BURG. J . Am.. Chem. Soc. 83, 2226 (1961). ,/ 3. L. R. GRANT. Ph. D.• dissertation, University of Southern C a l i f o r n i a . June 1961. 4. C. G. KRESPAN. J . Am. Chem. Soc. 83,. 3432 (1961). 5. W. R. CULLEN. Can. J . Chem. 38, 439 (i960). 6. If. M. BEG and H.C. CLARK. Can. J„ Chem. 39, 564 (1961). 7. M . M. BEG and H.C. CLARK. Can. J . Chem. 40,, 283 (1962). 8. H. D. KAESZ,•J. R. PHILLIPS and F. G. A. STONE. Chem. and Ind. 1409 (1959). 9. R. D. CHAMBERS, H. C. CLARK and C . J . WILLIS. Chem and Ind. 76 (1960). 10.. AUGER. Compt. Rend. 142,, 1153 (1906). 11. E..E. LEWIS and BL A.. NAYLOR. J . Am. Chem. Soc. 69, 1968 (1947). 12. R. N. HASZELDINE. J . Chem. Soc. 2508 (1952). 13. J . W. B. RES30R and G. F. WRIGHT.. J . Org. Chem. 22,, 382 (1957). 14... GERMAN PATENTS, 20.6057, 254187. 15. W. R. CULLEN, D. S. DAWSON, N. K. HOTA and G. E. STYAN. Chem. and Ind. In press. 16. W. R. CULLEN. Private communication. 17. P. M.•TKEICHALy E. PITCHER and F. G. A. STONE. J . Inorg. Chem. I, 511 (1962). 18. MASCHMANN. Ber. 59,, 13 , 11.42, 1148 (1926). 19. E. G. WALASCHEWSKI. Ber. 86, 272 (.1953). 20. H. J . EMELEUS, R. N. HAS2H3LDINE and E.G. WALASCHEWSKI. J . Ghem. Soc. 1552 (1953). 21. R. N. HASZELDINE and B. 0. WEST. J . Chem. Soc. 3631 (1956). 22. J . L. BOSTON, D. W. SHARP and G. WILKINSON. J . Chem. Soc. 3488 (1962). 23. W. R. CULLEN. Can. J . Chem. 38, 445 (I960). 24. R. N. HASZELDINE and B. 0. WEST. J . Chem. Soc. 3880 (1957). 5' H D K ESZi S. L. STAFFORD and F. G. A. STONE. J . Am. Chem. Soc. 81, 6336 (1959). 

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