Cleavage of vicinal diols by iodine triacetate and iodine(I) acetate

摘要

1978 1483 Cleavage of Vicinal Diols by Iodine Triacetate and lodine(i) Acetate By Richard C. Cambie,' David Chambers, Peter S. Rutledge, and Paul D. Woodgate," Department of Chemistry, University of Auckland, Auckland, New Zealand Oxidative cleavage of vic-diols is achieved rapidly and in high yield with iodine triacetate or iodine(i) acetate. Acetic acid and a macrocyclic peroxide have been isolated from the reaction of cis-cyclohexane-1,Z-diol with iodine(i) acetate in dichloromethane, suggesting that the cleavage occurs by a radical process. THEoxidative cleavage of vic-diols by reagents such as (diacetoxyiodo) benzene which contain iodine in one of its higher valency states, has been examined by a number of ~0rkers.l.~ Recently, we reported the preparation of iodine triacetate from iodine trichloride and silver(1) acetate and its regio- and stereo-specific addition to alkenes.We now report on its role and that of iodine(1) acetate as oxidants of vic-diols. The products from the action (stirring for 2 min at 20 "C) of iodine triacetate (1 mol. equiv.) in acetic acid on a series of vic-diols are given in the Table together with their isolated yields. New compounds were identified from their spectral parameters and where possible, by microanalyses of the parent or of a suitable derivative (see Experimental section). Iodine trichlor- ide alone in acetic acid did not cause oxidative cleavage and its action on cis-cyclohexane-l,2-diol(1), for example, resulted in acetylation to give the corresponding diacetate (3).7 Oxidative cleavage of the aic-diols also Cleavage of diols with iodine triacetate Yield ("/) 63 78 94 92 93 93 86 85 100 93 95 a Isolated as the 2,4-dinitrophenylhydrazone,m.p. and mixed m.p.128'. occurred at a similar rate if iodine(1) acetate, prepared from equimolar quantities of iodine and silver(1) acetate, was used instead of iodine triacetate. Oxidative cleavage of cis-cyclohexane-l,2-diolalso occurred if the iodine(1) acetate was prepared from iodine(1) chloride and R. Criegee and H. Beucker, Annulen, 1939, 541, 218. P. S. Raman, Proc. Indian Acad. Sci., 1956, MA, 321 (Chem. Abs., 1957, 51, 8010).A. Goosen and H. *4.H. Laue, J. Chem. SOC.(C), 1969, 383. S. Spyroudis and A.Varvoglis, Synthesis, 1975, 445. S. 3. Angyal and R. J. Young, J. Amer. Chem. SOC.,1959, $1, 5467. R. C. Canibie, D. Chambers, P. S. Rutledge, and P. D. Wood- gate, J.C.S. Perkin I, 1977, 2231. S. Winstein and R. E. Buckles, J. Amer. Chem. Soc., 1942, 64, 2780. a P. Lerivereiid and J. Conia, Bull. SOC.chim. France, 1970, 2715. 9 R. C. Cambie, G. J. Potter, P. S. Rutledge, and P. D. Woodgate, J.C.S. Perkiia I, 1977, 530. silver(1) acetate but the diol was unaffected after treat- ment with iodine(1) chloride and thalliuni(1) acetate l3 at 20 "C for 5 days. The reactions of either trans-cyclohexane-l,2-diol (2) or of 5~~-androstane-2P,3~t-diol (10) with the iodine-silver(1) acetate (1: 1) reagent gave both starting material and the respective dialdehydes in a ca.1 : 1 ratio, and it was necessary to use ca. two mol. equiv. of the reagent in order to achieve quantitative cleavage. Comparative t.1.c. examination of the reaction of cis-cyclohexane-l,2-diol with iodine(1) acetate (1 mol. equiv.) indicated the formation of hexane-lJ6-dial (16) and another compound which was converted completely into the dialdehyde (16) on treatment of the mixture with additional iodine(1) acetate (1.5 inol. equiv.). This intermediate, together with acetic acid, was isolated from a reaction carried out in dichloromethane. From spectroscopic and microanalytical data the intermediate was identified tentatively as the perhydrotribenzotetra- oxecin (26), a stable l4 crystalline peroxide (cf.ref. 15). Formation of this macrocycle was not detected during analogous reactions with the trans-diol (2). Criegee has postulated a cyclic mechanism for the oxidative cleavage of vic-diols with (diacetoxyiodo)-benzene but presumably this is not the case with iodine triacetate since the trans-diaxial diol (10) was cleaved readily to the dialdehyde (19). The isolation of acetic acid from the reaction of cis-cyclohexane-l,2 did with iodine(1) acetate in dichloromethane is consistent with clbsol;eavage via a radical pathway involving a hypoiodite.16 As indicated above, we showed earlier that ireatinent of cyclohexene with iodine zriacetate prepared from iodine trichloride and silver(1) xetate gave a mixture of the trans-iodo-acetate (4)(45yo)and tram-iodohyclrin (5) (10).During the present work, treatment of cyclohexene with iodine trichloride (1 mol. equiv.) and the cheaper and more soluble (in acetic acid) thallium(1) lo B. F. Bowden, R. C. Cambie, and J. C. Parnell, -4ustva2. J. Chem., 1975, 28, 91. l1 A. McKillop, R. A. Raphael, and E. C. Taylor, J. Oig. Claem., 1972, 37, 4204. l2 P. 111. Hardy, A. C. Kicholls, and H. N. Rydon. J.C S. Pr:.kin 11, 1972, 2270. l3 R. C. Cambie, W. I. Noall, G. 3. Potter, P. '3 Rutltdge, and P. D. Woodgate, J.C.S. Perkin I, 1977, 226. l4 D. Swern, ' Organic Peroxides,' Wiley-Interscience, New York, 1971, vol. 11, p. 583. l5 P. R. Story, B. Lee, C. E. Bishop, D. r).Denson, and P. Busch, J. Org. Chem., 1970, 35, 3059. l6 T.R. Beebe, B. A. Barnes, K. A. Bender, A. D. Halbert, R. D. Miller, M. L. Ramsay, and M. W. Ridenour, J. Oig. Ckein , 1975, 40, 1992. 1484 J.C.S. Perkin I acetate (3 mol. equiv.) gave the trans-iodo-acetate (4) gave the trans-iodo-acetate (4) (42) but in addition in 79 yield. However no cleavage of cis-cyclohexane-formed the trans-iodo-chloride (6) l3 (42).1,2-diol occurred with this reagent after 24 h at 20 "C EXPERIMENTAL General experimental details are given in ref. 17. General Procedure for Oxidative Cleavage of vic-Dio1s.-(a) With iodine triacetate. Iodine trichloride (1.78 g, 7.6 mmol) was added rapidly to dried acetic acid (25 ml) under nitrogen and the mixture was stirred at 20 "C until all solid had dissolved. Dried silver(1) acetate (7.6 g, 45 mmol) was(2 1 R'= RLOH, P=H added and the yellow suspension was stirred for 10 min,(3 1.R'= R2= OAc,R3= H (7) R=H centrifuged, and the clear liquid decanted under nitrogen. (4I R'=OAC,R*= H,R~=I (8) R=CH3 The molanty of the solution (equivalent to an 84 con-(5) R~=oH,R~=H,RLI centration of PI) was determined by addition of an (6) R'=Cl, R2=H, R3= I excess of potassium iodide to a portion and titration with standardised sodium thiosulphate solution under nitrogen. A portion (5 ml G 1.01 mmol) of the iodine triacetate solution was added rapidly under nitrogen to the diol (ca. C02Me 1.0 mmol) and the mixture was stirred at 20 "C for 2 min. The red solution was poured into ice-water, extracted with ether, and the extract was washed successively with water, saturated aqueous sodium hydrogencarbonate, water, HO" bsol;,A saturated aqueous sodium disulphite, and brine.SolventHo*-ewas removed from the dried solution under reduced pressure R~=CH~ to give the crude product which was purified by p.1.c.(9 R~=H,~2 =OH (11) RLH, (10) R'=oH,R*= H (12)R~=cH~,R*=H (b) With iodine(1) acetate. Freshly ground iodine (0.19 g, 0.75 mmol) was added over 20 min at 20 "C to a stirred R' R~C-CR'R* OCH (CH214CHO solution of silver(1) acetate (0.125 g, 0.75 mmol) in dried (16) acetic acid (5 ml) under nitrogen. The mixture was stirred OH OH for 10 min and the diol (0.3 mmol) was then added. The =CH, reaction was quenched after 2 niin and worked up as in(13) RLR* (14) R1=H, R2=Ph (a)* Hexane-l,8dial (16).-This had vrnaX. 1725 cm-l (CO),(15) R'= R2=Ph A,, 277 nm, 6 (cf.ref. 12) 1.48-1.77 (m, 2 x CH,), 2.26-2.63 (m, 2 x CH,), and 9.71 (distorted t, 2 x CHO), m/e 96 (M+' -HZO).(Z)-1,2,2-Trimethylcyclopentane-1,3-carbaldehyde (17).-'R This was an oil, b.p. 80" at 0.75 mmHg, vmx. (CCl,) 1725 (17) R=CHO cm-l (CO), 6(CC14) 0.90-2.95 (m, 2 x CH,, CH), 1.00 (s, 2-CH3), 1.12 (s, 2-CH3), 1.29 (s, 1-CH,), 9.66 (s, 1-CHO), and (18) R =COCHj 9.75 (d, J 2 Hz, 3-CHO) ; bis-2,4-dinitrophenylhydrazone, m.p. 273-274" (Found: C, 49.5; H, 4.6; N, 20.7. C22-R~CR~ H,,N808 requires C, 50.0;-H, 4.6; N, 21.2), m/e 528110 (M+')and 332 (M+' -C,H,N,O,). (22) R' = R2 =CH3 (2)-1,3-Diacetyl-1,2,2-trimethylcyclopentane ( 18).-ThisRlamp; (23)R' =Ph,R2=H was an oil, b.p.80" at 0.75 mmHg, v,,,. 1700 cm-l (CO), 6 0.62-3.00 (m, CH,, CH), 0.70 (s, 2-CH,), 1.13 (s, 2-CH3),(24)R' =R2 =Ph 1.30 (s, l-CH,), and 2.08 (s, 2 x MeCO), m/e 196 (M"), 153 (M+' -CH,CO*), and 110 (M+' -BCH,CO*); bis-semicarbazone, m.p. 197-198.5", m/e 251 (Mt' -NH-OCH flco2Mel7eP2ACONH,) and 236 (M+' -NHNHCONH,) ; bis-2,4-dinitro-phenylhydrazone, m.p. 153-154". A satisfactory analysis 14 0l3 was not obtained. '5 12H06 2,3-seco-5a-Androstane-2,3-dial( 19).-This was a viscous (20)R'=H, R2=CH3 "Q8 oil (Found: C, 78.8; H, 10.55. C1,H3,02 requires C,10 (21) R'=CH3,R2=H 78.6; H, 10.4), vmX. 1724 cm-l (CO), 6 0.71 (s, lS-H,), 0.84 (s, 19-H,), and 9.58-9.86 (m, 2 x CHO), m/e 290 (M+'),and 246 (M+' -CH,:CHOH).(cf. ref. 11). Treatment of cyclohexene with thallium(1) Methyl 2,3-Dioxo-2, 3-seco-olean-12-en-28-oate (20).-This acetate and iodine trichloride in a 1 : 1 molar ratio also was an unstable oil, b.p. 180-190" at 1 mmHg, 6 3.55 (s, OMe), 5.25 (m, Wl,, 9 Hz, 12-H), 9.53 (s, 3-CHO), and 9.76 l7 R. C. Cambie, R. C. Hayward, B. G. Lindsay, A. I. T. Phan, (distorted t, 2-CHO), m/e 484 (M'.), 466 (IM" -H,O),P. S. Rutledge, and P. D. Woodgate, J.C.S.Perkin I, 1976, 1961 ; R. C. Cambie R. C. Hayward, J. L. Roberts, and P. S. Rutledge, and 424 (M+' -HOAc). zbzd., 1974, 1858. Methyl 2,3-Dioxo-2,3-seco-urs-12-en-28-oate (21).-This was an unstable oil, 6 3.65 (s, OMe), 5.25 (distorted t, 12-H), 9.64 (s, 3-CHO), and 9.88 (distorted t, 2-CHO), m/e 484 (iM+'),466 (M+*-H,O, and 424 (M+' -HOAc).Reaction of cis-Cyclohexane- 1,2-diol wath Iodine Trichlor- zde.--The czs-diol (1) (92 mg, 0.8 mmol) was added to a solution of iodine trichloride (0.21 g, 0.89 mmol) in acetic acid (5 nil) and the mixture was stirred at 20 "C for 24 h. Work-up and p.1.c. (hexane-ether, 3 : 2) gave cis-cyclohexan- 1,2-diyl diacetate (3) l7 (88 mg, 557/,), 6 1.16-2.34 (m, CH,), 2.01 (s, 2 x OAc), and 4.95 (m, W11211 Hz, 2 x CHOAc). Reaction of cis-Cyclohexane- 1,2-diol wzth Iodine( I) A cetate in DichZoronzel'hane.-The cis-diol (1)( 1.22 g, 10.5 mmol) was added to a solution of iodine (2.76 g, 10.5 mmol) and silver(1) acetate (1.74 g, 10.5 mmol) in dichloromethane (40 ml) and the mixture was stirred at 20 "C for 10 min.Work-up yielded an oil (1.21 g) which was separated by p.1.c. (ether- hexane, 7 : 3) into starting material, acetic acid, and per- Z~ydrotribenzo~'t-,e,htetraoxecin(25) (0.46 g) which crystal- lized from ethanol-ether as plates, m.p. 86-87" (Found: C, 69.9; H, 10.1. C,,H,,O, requires C, 69.6; H, 9.70amp;), Y,,,. 1 130 cm (-0-),6 1.02-1.95 (m, CH,), 3.95 (m, W1,, 9 Hz, 5-,7-,12-,14-H), and 4.95 (distorted t, 19-,252-H), wz/e 310.213 4 (Mf'), 309.206 0 (Mt' -H), 213.148 0 1485 (M'. -C,H,O), 211.132 8 (M" -C,H,,O), 196.145 8 (M'. -C,H,,O,), and 98.073 1 (M'. -C,,H,,O,), 6~. 21.2 (C-Z,-13,-16,-17), 24.9 (C-9,-10), 28.9 (C-1,-4,-15,-18), 35.8 (C-8,-11), 74.8 (C-5,-7,-12,-14), and 104.5 p.p.m.(C-19,-22). Reaction of Cyclolzexene with Iodine Trichloride and ThaZlium(I) Acetate.-(a) Usi~ga 1 : 3 ratio. Thallium(1) acetate (5.0 g, 18.9 mmol) in dried acetic acid (10 mi) was added dropwise under nitrogen to a solution of iodine trichloride (1.42 g, 6.1 mmol) in dried acetic acid (15 ml) and the mixture was stirred at 20 "C for 30 min. The result- ing suspension was centrifuged and a portion (5 ml) of the clear solution was stirred with cyclohexene (99 mg, 1.2 mmol) at 20 "C for 10 s. Work-up gave trans-Z-iodocyclo- hexyl acetate (4) (0.26 g, 790/) (correct lH n.m.r. spec- trum) ., (b) Using a 1 : 1 ratio. Cyclohexene was treated as in (a) with a solution prepared from thallium(1) acetate (2.0 g, 7.6 mmol) and iodine trichloride (1.77 g, 7.7 mmol). Work-up and p.1.c. of the crude product gave tmns-2-iodocyclo- hexyl acetate (4) (0.29 g, 42",) and trans-l-chloro-2-iodocyclohexane (6) (0 26 g, 42O/;) (correct lH n.ti1.r. spectrum)., 8/105 Received, 231d Jatzuayy, 19781