Document gaqqV0kn2wnoGkDKjJOk0QkV

E. T DU POHT DE HEMO0RS & UCMBMTr PIGMEHTS DEPARSCMEiW Sg vial Mo. KB-69-13 Copy Tow wtipcm p l an t PXQIW COLORS RESEARCH REPORT SUBJECT: PYRIDOKOqijflHOLOWE - INTERIM REPORT PERIOD COVERED 2 September, 1968 ~ May, 1969 Date 5 11/6/69 SERIAL N0 ,, KN-69-13 DUP050081602 E. I. BIT POUT BE NEMOURS & COMPAQ PIGMENTS DEPARTMENT KN-69-13 Copy -*o.tJ2X DISTRIBUTION; 1, Research Numerical File - 223 2. Research Office File - 223 M. Hunt/E, Gonick Wo So Struve 5. F. F. Ehrich/E. F( Klenke/B, H. Perkins/ Newark Library 6, W. Jo McClure/R, A, Hageman P. Jo Monahan (Vital Records) Eo L, Rodowskas/R. M, Salem! 9- H. Ro Linton 10 o R,, Z, Fortney/D. S. Watson iial. R. Ho Wetzel J. W. Minnich 13. J, F,, Maurer 1^. W A. West .15- Jane E. Macrum 16 E. E. Jaffa, Newark !7o R, Jo North 18. ExItI ra ...19- 20 21 22 IT U IT HOT MT SUBJECT: PIGMENT COLORS RESEARCH REPORT ammii mi . i ic."i r.riii-t n Jutm+itaaf* PYRIDONOQUINOLOiffi ~ INTERIM REPORT PERIOD COVERED: September, 1968 ~ May, 1969 SUBMITTED BY: R. J. NORTH DATE SUBMITTED; 9/26/69 APPROVED BY; W. A. TOT DATE RELEASED: H/6/69 ABSTRACT s The synthesis of pyridonoquinolpne and related compounds was undertaken to evaluate their potential as ixghtfast yellow pigments. 3 rs; Rtv ^ KTi 1 ArKSOH ij\yl So> > '** A1' Hit ** r r o o m DUP050081603 TABLE OF CONTENTS I. INTRODUCTION ix. smmm ah d c o n c l u s io n s III. PATENT SITUATION IF, HISTORY V. DISCUSSION 1. Synthesis of Pyridonoquinolone 2. Alternate Attempts to Synthesise PQ 3. Synthesis of N^-Bibenaylimide of PyridonoquinoioriS 4. Synthesis of Diaeenaphthyl Derivative of Pyridottoquinolone VI. EXPERBIENTAL VII. BIBLIOGRAPHY PAGE 1 i I 1-2 2-5 2-7 7-8 8-9 9-14 15 DUP050081604 FYRIDQIJOQUINOLONE - INTER214 REPORT iM.nimui'imwiiii^H fi ii 'W--?p 'nnaw>miwiwr*np>nfr1.'ri-wtwnM>tWiii>nMn,iinHiim nrrrnr^~nr->a''n,nini>mii I. II. , III. IV o INTRODUCTION To completely round out the DuPont pigment product line a strong, lightfast yellow is required. Many areas of synthetic organic chemistry have been explored in an attempt to obtain a suitable candidates particularly the area of pyridone chemistry, in which the lightfast red pigment, quinacridone, was discovered. One approach, which has not been attempted and is the objective of this program is to synthesise an analog of quinacridone poss essing no peripheral benzene rings. This compound, pyridonoquinolone (PQ), should possess the same hydrogenbonding characteristics as quinacridone, which are known to be essential for lightfastness, and hopefully might exhibit color in the desirable yellow region of the spectrum. To this end, the synthesis of pyrldQnoquinolone and some related derivatives was undertaken. SUMMARY AND CONCLUSIONS KwWWMWl*****--Jcitn.l MnM' Pyridonoquinolone (PQ) has been synthesized and found to be a tinctorially weak, relatively insoluble, greenish-yellow pigment, the lightfastness of which is presently being determined. It is concluded that in order to obtain the desired color in the reddish-yellow reason, auxochromic substitution is necessary on the pyridone rings. The N,N!-dibenzylimide of PQ tetracarboxylic acid was synthesized and found to be a tinctorially attractive yellow-orange compound being too soluble, however, for use as a pigment. To decrease the solubility and yet retain the desired color characteristics, the unsubsti tuted diiraide is being prepared. A yellow-orange diacenaphthyl derivative of PQ was also synthesized. Additional material is being prepared for complete pigment evaluation studies. PATENT SITUATION No patent applications based upon this work is warranted at present, HISTORY References to the diazaanthracene ring system first appeared in the literature in 1939 . The common name used for the ring system is 1,5-anthrazoline but Chem, Abstracts prefers pyrido (2,3-g) quinoline and this nomenclature and numbering system is used throughout this report. Only DUP050081605 -2- IV HISTORY (Cont'd) a small number of derivatives have been reported2. 2 3 pyrido (2,3-g) quinoline but it appears that the 4,9-diketo derivatives which are the subject of the present study are unknown in the literature and thus represent a new class of compounds. V. DISCUSSION 1. Synthesis of Pyrldonoquinolone Two main factors made the synthesis of pyridonoquinolone an attractive project. One# Nelson^ synthe sized octal lydroquinacridone. (I) and found it to be a fairly strong yellow#- non-.light.fast compound; the lack of lightfastness is probably a function of the non-coplanarity of the fused cyclohexene rings which adversely affect efficient intermoleeular hydrogen bonding. Since the cyclohexene rings are not chromaphares, but probably act as auxochromes, their removal was expected to cause a very slight hypsochromic shift in the absorption spectrum and thus retain the desired yellow color in the resulting pyrldonoquinolone molecule. Secondly, Luttke and Hermann* t" molecular orbital (MO) calculations showed that removal of the peripheral benzene rings in thioindigo, should cause the longest wavelength visible band at 5^3 my/ to undergo a hypso chromic shift of about 50 m/*- in the resulting bisthiophen indigo (XI). Experimentally, II was actually DUP050081606 3V. DISCUSSION (Cent fd.) S thioindigo 543 m/* // o A max. 502 m/A shown to exhibit long wavelength absorption at 502 ra/>in excellent agreement with the MO calculations. If both of the above considerations were applicable in the pyridone system* removal of the two peripheral benzene rings in quinacridone should result in a hypso- chromic shift from 515 m/x (QA) to 470 a desirable red-yellow region for Pc. The synthesis was accomplished 0H 0H max, 515 myA p\ max. 412 m and it was found that the long wavelength absorption of PQ occurred at 412 m^ in the greenish-yellov? region indicating that an unexpectedly large hypsochromic shift of ~100 m/* had occurred. A reasonable interpretation of this result is that the peripheral benzene rings in QA contribute to a greater extent to the chromophore than is the case in thioindigo^ in other words* the benzo substi tuents exert a greater auxochromie influence on the electron deficient six-membered pyridone rings than on the electron rich five-merabered thiazolone system. The synthesis of PQ was accomplished in four steps starting with a ls2MIehael addition of diethyl-2*5~diamino~ terephthalate (III) to dimethyl acetylene-dicarboxylate (.17). DUP050081607 4- DiscussxoK (contra) 1. Synthesis of Pyrldonoquinolone- (Cont ?d) The product (V), a bis-fumarate adduct, was obtained in COOEt _COOMe MeOOC. CH it HeOOd^HN COOEt NHa TX'OMe IV EtOOG COQMe it /k H MeOOC good yield, and was characterized by its ir and nmr spectra. The transoid geometry of the molecule was demonstrated by its single vinyl C-.H absorption in the nmr at 5.52 ppm., in good agreement with other work? published on anilino-fumarates. Y NaOMe Dieckmann cycllsatipn of V, employing sodium methoxide, produced a symmetrical tetraester (VI), which was characterized by elemental analysis and its pmr spectrum. The ir spectrum did not display characteristic C~0 absorption of 4-quirjolones.-' This is analogous to similar observations made with other 4-quipolones ^ substituted in the 2,3 positions with bull^ pubstituents. This particular reaction is of interest (since it provides a general facile synthesis of 2,Sr-djicarboalkoxy- <minolin-4~ones and 2,3,7,8-tetracarboalko^y pyrido (%*3"g) quinolin-4s9-diones, both new classes of compounds. MeOOC MeOOC CQQH DUP050081608 -5V, PXSCUSSXOM (Cont *d) 1. Synthesis of Pyridonoquiriolone (Cont *d) Complete saponification and partial decarboxy lation of VI was accomplished by refluxing the ester in ethylene glycol with the theoretical amount of potassium hydroxide. The product (VII) was a diacid3 in which the positions of the two carboxy groups has not been unequivocally established. Finally, thermal, decarboxylation of the diacid VII was accomplished by heating at 28oC in tetramethylene sulfone to yield the desired pyridonoquinolone (PQ). PQ was found to be twice as soluble as QA in boiling DMP, 0.50 g./l. vs. O.25 g./l., and tinetorially a weak greenish-yellow having a long wavelength absorp tion at 412 m>c (i 19,900). The lightfastness is presently being determined,and although the compound does not appear to be of interest as a yellow pigment, it will be evaluated as a W absorber. In addition, it will be of theoretical interest to see the effect of the absence of the peripheral benzene rings on lightfastness. 2, Alternate Attempts to Synthesize PQ, In an effort to obtain a diester rather than tetraester intermediate for subsequent ease of saponification and decarboxylation, diethyl-2,5- VIII DUP050081609 6- V. DISCUSSIOH- {Cont'd-} 2. Alternate Attempts to Synthesize PQ {'Cont Td) diaminoterephthalate was condensed with ethylpropiolate in a Michael addition to-yield the bis-adduct VIII. Attempts were made to cyclize the bis-adduct VIII via a Dieckmann reaction to obtain IX and by a ConradLimpach cyclinzation to obtain the diester Xj none of the attempts proved successful. Conrad-Limpach cyclization of the bis-adduct V produced the tetraester XX3 which resisted all efforts "CQQMe of saponification under alkaline and acid conditions. Ring opening may have occurred under these stringent reaction conditions. A dichloro Michael adduct (XXI)5 prepared by Michael addition of dimethylacetylene dicarboxylate and 2,5-dichloro-p-phenylene diamine, was successfully DUP050081610 -7V, DISCISSION (Cont5 cl} 2. Alternate Attempts to Synthesize PQ (Cont *d) eyelized in boiling Dowtherm to yield- the 5,10diehloro - 2,7-diearbometb.oxy derivative of PQi Further work was interrupted since the desired PQ was obtained concurrently-by successful decarb oxylation of the diacid VII. However, this approach appears to be another reasonable route for the synthesis of PQ and its 5j 10-substitu.ted derivatives. 3- Synthesis of the N,PI;-Dibenzylim3.de of PQ - Tetra- CaxBoxyI3^r^xH~"~~ . In an effort to enhance the weak yellow absorption exhibited by the symmetrical tetraester VI, the N,N'dibenzylimlde (XIV) was prepared and found to be a bright yellow-orange solid, with absorption maxim at 485 m/A (, 16,620) and 455 mx (t 17,l60). However, due to excessive solubility, the compound is not an attractive pigment candidate. For this reason the unsubstituted diimide (XV) is being prepared in the hope of maintaining the desirable visible absorption characteristics while decreasing the solubility. The diimide represents a new ring system, not listed in Chem. Abstracts or Patterson's Ring Index. A tentative number system and name based upon Chem, Abstracts guidelines for nomenclature is; DUP050081611 -8. DISCUSSION (Cont jdY 3* Synthesis of the NjN'-Dibenzylimide of Pa- Tetra- )oxylicAc id (Con:T?a)^^^ 2H98H-dipyr:rolo {3j4-e<s 3f,45~e') benzo (1,2-b: 4,5-b*) dipyridine 4. Synthesis of the Dlaeenaphthyl Derivative of PQ, Two yellow derivatives of the PQ ring system, the 2,7-diphenyl (XVI) and the 2,3,7,8~tetraphenyl (XVII) analogs were synthesised at Newark and both were Shown to have poor lightfastnessf. A reasonable explanation for this lightfastness deficiency is based on the assumption that the phenyl rings, which have complete freedom of rotation, interfere with efficient intermolecular hydrogen bonding. It was thought that by fusing the benzene rings in XVII, keeping symmetry considerations in mind, the resulting coplanarity might favorably affect lightfast ness. To this end, the diacenaphthy! derivative (XVIII) DUP050081612 O lo -9- V* DISCUSSION (Contra) 4. Synthesis of the Dlacenaphthy1 Derivative of PQ (Cont!d) by condensing acenapthenone with diethyl - 2,5-diaminoterephthalate followed by pyrolysis in refluxing Bowtherm. A small amount of a yellow-orange solid was obtained which after acid recrystallization showed an ir spectrum suggesting the formation of XVIII. More material Is being prepared for a complete charac terization and pigment evaluation. The diacenaphthyl derivative also represents a new ring system not listed in Chem. Abstracts or Patterson * s Ring Index and a tentative name and numbering system based upon Chem Abstracts guidelines of nomenclature is; 14 15 1o 11 10 65 diacenaphtho (1,2-e; l5,2*-e,)) benzo (1,2-bs 4,5-bf) (methoxycarbonyl) - NB-1904-9 (RJN) NB-1847-32 (EEF) A solution of 12.6 g {0.05 mol) of diethyl - 2,5-diamino-terephthalate and 15.6 g (0.11 mol) of dimethylacetylenedicarboxylate in 125 ml anhydrous methanol was refluxed for five hours. During the reflux period a yellow solid came out of solution. The hot mixture was filtered and the yellow solid washed with methanol to yield 18.5 g {69#) of yellow crystals, mp. 175-178 (EE3 1847/32, mp. 178-179). Recrystallization from 185 ml methanol and 90 ml DMF yielded 13.5 S yellow solid mp. 178-1793 ir (Nujol) 1740 (C=0), 1720 (0-0), 1680 (0=0) and 1600 cm~J-(CC)| W and visible spectra (DMP)JAmax. 401 ( 18,500), 350 (21,300) and 263 (13,500)3 ninr (DMSO-d6) 1.48 ppm DUP050081613 -10- VI, EXffERBffilfTAL {Cont'd) (t,6,-0-CHsgH9), 3-73 (d,12,~0CHsh 4.37 (q^-OpKaCHa), 5*52 (5,2, vlnyli=C-H), 7.24 (s,2, aromatic C-H), and 10*90 ppm (s,2, n -h 7. Anal. Calc !d for 03^28*0l2j C, 53-70; H, 5*22; N, 5.22 Found: C, 53*76; H, 5*335 H, 5.28 2 Preparation of 2,3,7,8~ te tracarbomethoxy-pyrido (2,3-k )* quinolS^ J*i*nw^iW<iiirtrirwiiwTtWii'intrrTnrnrirTrTirT,-i*`ii-i nimTii, .Mmifiii r rwii i>f ,1,1 1904-26 (RJN) 1847-37 (EEF) To a stirred solution of 1.38 g (0.06 mol) sodium metal in 30D ml of anhydrous methanol, 16.08 g (0.03 mol) of diethyl-2,5-bis p.,2-bis (methoxycarbonyl)~ vinyl amino] terephthalate (V) was added. Solution occurred at 50 with a yellow solid precipitating at 60. The .mixture was refluxed for four hours and filtered hot. The dry yellow solid was dissolved in water, and acidified with glacial acetic acid to yield 15 g crude yellow solid after drying. Recrystallisation from DMF yielded 13 g (97.5$) of a yellow powder, mp. 330-340 (d.) (EEJ 1847/37, mp. 330-340 id.)); ir (Nu,1ol") 1750 fC=0k I6IO and 1540 cm"x (ring); W and visible spectra (DMF) /\max. 445 m>c (t 7600), 424.(0050), 375 (16,100) and 269 (26,000); nmr (DMSO-d) / 3.75 ppm (9,6, HH-C-COOCHs), 3.90 (s,6, O-C-C-COOCH3). 8.70 (s,2j' aromatic C-H), and 12.60 ppm (s,2><W~H). Anal. Calc`d for C20Hi6NaOios C, 54.00; h, 3-61; H, 6.31 Found: C, 54.75; H, 3.72; fif, 6.24 3. l!^^4ig^^ft^c^bogypyrddo_j(gjt3m&1.2auj!jlQ3d!ne^jLi-9 7XHV oHf-dione IVlX1. -----............................ A 1904-420 (RJN) A mixture of 4.84 g (0,0109 mol) 2,3,7,8-tetra- earbomethoxypyrido (2,3-g) quinolin-4,-dione, 2.96 g (0.0643 mol) potassium hydroxide in 100 ml ethylene glycol was refluxed at lo5~190C for six hours. The yellow-orange solid which had precipitated out. during the reflux period was filtered, washed with water and dried. The dry solid was suspended in water, acidified with cone. HC1, filtered, washed acid-free and dried to yield 3 g yellow solid, mp, > 400C; ir (Uujol) 1695 (ao) and 1600 cm**1 (ring); W and visible spectra (DMF) /\max. 424 17,700) and 402 (11,000); neut. eq., ISO (theo. 150). DUP050081614 YI. 1- EXP3SRIMEHTAL {Gone! d) 3. (Contfd) Anal, calc'd for Ci4H8 IfeQg: C, 55-701 H, 2.67; M, 9 = 32 Found; C, 54.493 H, 2.81$ N, 9.11 4. Synthesis of pyrido (2.3-g) auinoline-4,9 {IH. 6H)- aionel p.yriaonoquxnoioneT. >wtiw'i u m ^X5tfJUriBrf>.ii>TiiiwnwA 1904/42D (RJH) A mixture of 5 g (0.0167 mol) dicarboxypyrido (2,3-g)quinolin-4,9-dione in 75 ml tetraraethylene sulfone was stirred and refluxed for eight hours, the mixture changed color from orange to greenish-yellow. The mixture was filtered hot, the solid washed with ethanol to yield 3 g greenish-yellow solid. Acid recrystallization yielded a greenish-yellow solid, insoluble in dil. NaHCOs, rap.> 400*0; ir (Nujol) 1605 cm~J- (C-C) and 1540 (ring); UV and visible spectra (DMF) 7\max. 412 ray (t 19>100) and 390 ( 15,300); solubility, 0.50 g/1 boiling DMF. In:.:., 1 ' V.* O^WaOsi 0, 6?.91$ H, 3.?9> N* 13-20 Found; C, 68.10; H, 3.853 N, 13-12 1904-32 (RtTK) A mixture of 4 g (00,009 mol) 2,3,7,8-tetracarbomethoxypyridc (8,3-g) quinoline-4,9-dione and 0,2 g (O.OO37 mol) ammonium chloride in 100 ml benzylamine was refluxed for six hours. The yellow-orange solid which had precipitated during the reflux period was filtered, washed with aqueous ethanol, and dried to yield 4.1 g of solid. Recrystallization from DMF yielded 3*8 g (56.8fo) yellow-orange solid, mp.>400C; ir (flujol) 1740 {C=0K 1710 (0=0) and 1630 cm" x (C=0); visible spectrum (DMF) /Muax. 485 &/U ( 16,620) and 455 (17,160). Anal, calc5d for C28Hl4R46 s c> 67,92| H, 3-42; N, 10.56 Found; C, 68.36; H, 4,17; W, 10.70 6. Preparation of Acenapthenone 1904-31 (RJW) A mixture of 142.3 g (0.762 mol) 1-naphthylacetic acid in 310 ml thienyl chloride was refluxed for six hours. Excess thienyl chloride was distilled off under water aspirator pressure never allowing pot temperature to exceed 150, 1-naphthyl acetyl chloride was then distilled at bp. 175-185 at 15-20 mm (lit. bp, 188 at 23 rm.) to yield 78,5 g (50>5$) clear yellow oil. DUP050081615 12" vt. EXBERIMEMrAL (ConVd) Cyelization to yield acenapthenone was accomplished by slowly adding a solution of 78.5 g (0.384 mol; oi l-n&phthylacetyl chloride in 75 ml dry nitrobenzene dropwise to a suspension of 56.4 g (0.42 mol) aluminum chloride in 500 ml dry nitrobenzene at 25 with stirring. The addition required 1-1/2 hours and when complete, the brownish mixture was stirred for six hours and allowed to stand overnight. The mixture was poured onto 1000 ml crushed ice and the contents were then steam distilled. After distillation pf all the nitrobenzene, acenapthenone distilled over it was filtered and dried to yield 20 g (31$) of white needles,mp. 118-120 (lit. mp. 120-121")j ir (Nujol) 1710 cm"1 (C-0). 7* Preparation of Diacenaphtho (1,2-e I 1 *-.2f-e*) bbee;nzo in.rfelMohe mm). 1904-45 (RJN) A mixture of 3*36 g (0.02 mol) acenepthenone and 2.52 g (0.01 mol) of diethyl-2,5-diaminoterephthalate in 75 ml Dowtherm was stirred and heated at 170 for one hour. The dark brown solution was then slowly heated to reflux (260C) and held there for four hours. The orange solid which had precipitated was filtered hot, washed with ethanol and hot DMF to yield 2 g yellow-orange solid. Acid recrystallization from 95$ HaSO* yielded 1.2 g yellow-orange solid, mp.p400C; ir (Mujol) 1660 (0-0), 1645 cm"1 (C=C); Jftf, 4.60 (theo. 6,08). 8. Preparation of 2,7-diearbomethoxY-5,10-dicayboethoxy' dione' 1904-23 (BJW) One gram (0.0018 mol) of well pulverized diethyl2,5-bis- [I,2-bls(methoxycarbonyl)-vinylaminoj t erephthalate (V) was added portionwise to 50 ml vigorously refluxing Dowtherm. The resulting solution was refluxed for 30 minutes, and turned light brown during that period The solution was then cooled and drowned into 100 ml ligroin with stirring. The resulting precipitate was collected, washed with ethanol to yield, after drying, 0.5 g of a tan solid. Recrystallization from DMP/EtOH yielded 0,25 g orange solid, mp, 25I-253 (d.)j DUP050081616 -13VI* SXaSBZME83EAt (Confc*d) Anal, calc'd for C22H20^a0l0J G* 56.00$ H, 4.26$ N, 5*97 Pound: C, 56.01$ H, 4,06$ N, 5.97 9. 1904-9 (RJK) 1847-67A (EEJ) A mixture of 12.6 g (0.05 mol) diethyl 2,5-diaminoterephthalate and 10.80 g (0.11 mol) of ethyl propiolate in 125 ml anhydrous methanol was refluxed for five hours. After cooling, the precipitated yelloworange solid was filtered, washed with cold methanol and dried to yield 14 g (62.5$) yellow solid, mp. 145165. Recrystallization from DMF/EtOH yielded 10 g orange solid, mp, 150-165 (EEJ 1947/67A, mp. 150-165)$ broad melting point suggest mixture of geometric isomers$ ir (Hujol) 1740 (C-0), 1690 (C-0) and 1615 cnr1 (C-C}$ w and visible spectra (DMP) 7\max. 420 m*x { 8500) and 351 (46,000). Anal, calc!d for C22&28sQ8% C, 59*00$ H, 6.25$ N, 6.25 Founds G, 59,00$ H, 6.4l$ N, 6.29 Preparation of diethyl-3,S-dichloro-2,5-bis fl,2-bis TEiethoxjre&PE'<^ " (XllH"' ~r A mixture of 3154 g (0,02 mol) 2,5-dichloro-pphenylene diamine and 5*68 g (0.04 mol) of dimethyl acetylene diearboxylate in 120 ml anhydrous methanol was refluxed for five hours. After cooling, the precipl DUP050081617 -14 VI , EXPERIMENTAL (Cont'd) 11. Preparation of '5. lO-dichloro-2. ^-dicarbomethoxs .one 1904-34 (RJN) Three grams (O.OC49 mol) of diethyI-3,6-dichloro2,5-bis [1;2-bis (methoxycarbony1)~vinylaminoj terephthalate (XIX) were added portionwise to 50 ml of vigorously refluxing Dowtherm. After coraplete addition* the yellow-brown solution was refluxed and stirred for an additional 15 minutes. The solution was cooled- and drowned into 100 ml ligroin. The precipitated yellow solid was collected and washed with methanol to yield, .after drying, 2 g of yellow solid, mp. 245250. Recrystallization from BMP produced & yellow solid, mp. 259"260j ir (Nujol) 1740 (C-O) and I69O cm"1 (C=0); mass spec, molecular ion at 395 2 (MW 337.17). Anal, calc5d for Ci6%0^acla06: C, 48.38; H, 2.535 7.06 Found: 0, 48.38; H, 2.63; N, 7.36 /me DUP050081618  15- VII. BXBLIOSRAPHY 1.. Ruggli and Preiswerk, Helv. Chim. Acta. 22. 478.(193.95- ~~ 2. Ruggli and Brandt, Helv. Chim. Acta 27, 274 (1944). 3. Kelson, Newark RN Report. 4. Littke and Hermanns, Ber. 101, 1708-14 (1968) 5. Heindel, Fish, and Lemke, J. Org, Chem. 33, 3997 (1968). 6. Kay and Taylor, JOS (C), 2656 (1968). 7. Matrick, H., Newark KH Report. 8. Buu-Hoi, Calgnant, Compt. Rend. (1942) 214, 315. DUP050081619