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The structure of the acenaphthene-1,2-diol dinitrates and their reaction with pyridine Csizmadia, Imre 1959

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THE STRUCTURE OF THE ACENAPHTHENE-1,2-DIOL DINITRATES AND THEIR REACTION WITH PYRIDINE by I M R E C S I Z M A D I A A Thesis Submitted in Partial Fulfilment of The Requirements for the Degree of M A S T E R OF S C I E N C E in the Department of CHEMISTRY We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA September, 1959 - i i -A B S T R A C T Calculation of bond angles from the available X-ray diffraction data for acenaphthene, indicated that the five-membered ring is planar and that cis-1.2-substituents are fully eclipsed and transsi.2-rsubstituents fully staggered in this ring system. These conclusions were confirmed by the ease of formation of cyclic car-bonate and isopropylidene derivatives of the cis-acenaphthene-1.2-diol and the failure of the trans-isomer to form these new derivatives* The presence of intramolecular hydrogen bonds in the crystalline cis-diol and the absence of such bonds in the trans-diol also supported this structure. A single carbonyl stretching frequency of 1718 cm"1 was found in the spectrum of pure acenaphthenequinone and the reported second band around 1770 cm * was shown to be due to an impurity. A linear relation of the C=0 and C-O-C stretching frequencies of the cis- and transj* diacetate and dibenzoate esters of the acenaphthene-1,2-diols was determined and compared with a similar relationship found for steroid esters. The dinitrate esters of the cis- and trans-acenaphthene-1.2-diols were prepared and characterized and the rates of their reactions with anhydrous pyridine were compared with!:those of other cyclic diol dinitrates. The dinitrates decomposed in a first order reaction with half lives of 90 and 610 minutes for the trans- and cis- isomers respectively at 25°C. - i i i A combination of chromatographic and spectrophotometry techniques was developed for rapid and accurate analyses of mixtures containing nitrate esters. An ultramicro-Kjeldahl procedure was developed for the determination of covalent nitrate nitrogen on a microgram scale* In p r e s e n t i n g 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 o f the requirements f o r an advanced degree at the U n i v e r s i t y o f B r i t i s h Columbia, I agree t h a t the L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r r e f e r e n c e and study. I f u r t h e r agree t h a t permission f o r extensive copying of t h i s t h e s i s f o r s c h o l a r l y purposes may be granted by the Head of my Department or by h i s r e p r e s e n t a t i v e s . I t i s understood t h a t copying or p u b l i c a t i o n o f t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l not be allowed without my w r i t t e n p e r m i s s i o n . Department of C£e**«'$>tiy  The U n i v e r s i t y of B r i t i s h Columbia, Vancouver $, Canada. Date <bct^ StC , A ) ^ ?  iv -ACKNOWLEDGEMENT I would like to express my sincere thanks and appreciation to Dr. L. D. Hayward for his continual advice and encouragement. Thanks are also due to Mr. E» Premuzic who checked the Russian translations, and to a l l the technicians of the Chemistry Department for their assistance. - v -Table of Contents Title i Abstract i i Acknowledgement iv Table of Contents v List of Figures vi List of Tables v i i i General Introduction 1 Historical Introduction 2 Nitrate Ester Chemistry 3 Acenaphthene Chemistry 11 Results and Discussion 25 Suggestions for Further Work 52 Experimental 55 A) Materials 56 B) Analysis 78 C) Spectra 85 D) Paper chromatography 87 E) The reaction of pyridine with the Acenaphthene-1,2-diol Dinitrates 89 Appendices 1) Calculation of Bond Angles of Acenaphthene 98 2) Infrared spectra of Acenaphthene Derivatives 100 3) Ultraviolet spectra of Acenaphthene Derivatives 118 4) Paper Chromatography of Acenaphthene Derivatives 124 References 126 - vi -List of Figures 1. The Carbon Skeleton of Acenaphthene 27 2. Bond Lengths of Acenaphthene — — —... 29 3. Molecular Model of Acenaphthene — -.—-.-....31 4. C=0 and C-O-C Stretching Frequencies in Esters of Acenaphthene-1, 2-dio Is — — — — - — — 39 5. Rate of Reaction of Cis- and Trans-Acenaphthene-1.2-diol Dinitrates with Pyridine at 25°C 47 6. Acenaphthene Cox Diagram— — 57 7. Acenaphthene Vacuum Distillation Apparatus- -57 8. Paper Chromatogram of Products from the Action of Phosgene on Acenaphthene-l,2-diols-- — — — — — — 68 9. Paper Chromatogram of Nitration products of Cis-Acenaphthene-1, 2-diol 70 10. Extraction of Dinitrates with Petroleum Ether — - — - 72 11. Paper Chromatogram of Products from the Reduction of Trans-Acenaphthene-1,2-diol Dinitrates with Metal H y d r i d e s - — - — 75 12. Paper Chromatogram of Hydrogenation Products from Dinitrates—77 13. Ultramicro Ammonia Distillation Apparatus————-----—-—-—81 14. Calibration Curve for Ammonia - Nessler's Reagent at 405 m — 8 3 5 P per Chr matograms of Ether Soluble P oducts of the Reaction of Cis-Acenaphthene-1.2-diol Dinitrate with Pyridine at 115°—91 16. Paper Chromatograms of Ether Soluble Products of the Reaction of Trans-Acenaphthene-1,2-diol Dinitrate with Pyridine at 115°-92 17. Paper Chromatograms of Ether Soluble Products of the Reaction of Cis- and Trans-Acenaphthene-1.2 diol Dinitrate with Pyridine at 25°, after 30 minutes 95 18. Calibration Curves Relating to Micromoles of Acenaphthene Derivative— — — ---96 - v i i -19. Geometry of Acenaphthene — - — - — — 99 20-30. Infrared Spectra of Acenaphthene Derivatives——-— ——107-117 31-35. Ultraviolet Spectra of Acenaphthene Derivatives 119-123 - v i i i List of Tables I Decomposition Rate Constants for Dinitrates 10 II Sum of the Internal Angles of the Hexagons in the 28 Acenaphthene Molecule III Atomic radii 28 IV Principal Infrared Absorption Bands of Acenaphthene 32 V Melting Points and Carbonyl Frequencies of Acenaphthenequinone 32 VI Hydroxyl Stretching Frequencies of Cyclic-l,2-diols 37 VII Isopropylidene Derivatives of Cis- and Trans-Cyclohexane-1,2-diol 42 VIII Acetonation of Trans-Acenaphthene-1.2-diol 42 IX Nitration of Cis- and Trans-Acenaphthene-1.2-diols 44 X RF values of Products from the Reaction of Pyridine with Cis- and Trans-Acenaphthene-1.2-diol Dinitrates 44 XI The RateAof Cis- and Trans-Acenaphthene-1.2-diol Dinitrates with Anhydrous Pyridine at 25.2 + 0.1°C 48 XII Rate Constants for the Decomposition of Acenaphthene-diol Dinitrates In Pyridine at 25.2 + 0.1°C 48 XIII Melting Points of Pure and Impure Acenaphthene-1,2-diols and Their Derivatives 51 XIV Yield and Melting Point of Crude Oxidation Product of Acenaphthene 60 XV Yield and Melting Point of Purified Oxidation Product of Acenaphthene. 61 XVI Standard Deviations of Ultraraicro Nitrogen Determinations 84 XVII Nitrogen Analyses on Isoidide Dinitrate 84 XVIII Data of Ultraviolet Spectra of Acenaphthene Derivatives 86 XIX Standard Deviations for Nitrate Ester Determinations on Paper Chromatograms 95 ix XX Characteristic Infrared Frequencies of Different Samples of Acenaphthenequinone 101 XXI Characteristic Infrared Frequencies of Pure and Impure Cis-Acenaphthene-1.2-diol 102 XXII Characteristic Infrared Frequencies of Pure and Impure Trans-Acenaphthene-l.2-diol 103 XXIII Characteristic Infrared Frequencies of Acenaphthene-1,2-diol Cyclic Derivatives 104 XXIV Characteristic Infrared Frequencies of Acenaphthene-1,2-diol Esters 105 XXV Characteristic Infrared Frequencies of Acenaphthene-1,2-diol Dinitrates 106 XXVI Modified Rp Values for Acenaphthene Derivatives 125 - 1 -GENERAL INTRODUCTION In this research acenaphthene derivatives were selected for study because the two carbon atoms in the fivemembered ring could be con-sidered as ethane carbons with fixed conformations. Free rotation of the carbon atoms is prohibited by the attached naphthalene nucleus. It was expected that the steric factors in the mechanism of reactions of functional groups on these two carbon atoms might be determined by exami-nation of the rates and products of the reactions. As a specific example the acenaphthene system was chosen for a study^nitrate ester-pyridine reaction. - 2 -HISTORICAL INTRODUCTION - 3 -Nitrate Ester Chemistry The nitrate esters are important both for their chemical interest and their widespread technical applications. Their technology is based on their uses as explosives, lacquers and drugs. In organic chemistry they have been extensively used in sugar synthesis and in the isolation and study of polysaccharides. In recent years development of the chemistry of free alkoxy radicals has thrown new light on the decom-position of these esters in ignition and detonation. Relatively l i t t l e is known, however, of their reactions in solution (1) . Preparation Organic nitrates are usually prepared either by direct esterification of the corresponding alcohol or by exchange reactions. These as well as several special preparations have been extensively reviewed (1) (2) (3) . The mechanism of O-nitration has a close relationship to C-nitration as has been established by Ingold and coworkers (4) and this relationship has recently been shown to extend to N-nitration (5) . These mechanisms have been reviewed recently by Topchiev (6) . Almost a l l the various preparative methods have been used by Hayward and coworkers in the preparation of nitrate esters. The alcohols were treated at 0°C with one or other of the following: nitric acid (100%)-sulfuric acid mixture (7) (8) (9) (10) (11); nitric acid-acetic anhydride-acetic acid mixture (12) (13); nitrogen pentoxide in the gaseous state (14) as well as in chloroform solution (15) and nitric acid with phosphoruspentoxide (15) - 4 -A l l these preparative methods are direct esterifications and are now well known and widely used* Less frequently used are the exchange methods such as the methathesis of organic halide compounds with silver nitrate (3) using organic solvents* In some solvents (such as acetonitrile) the reaction proceeds homogenously and in others (ether, benzene, nitrobenzene, nitro-methane) heterogenously. It should be mentioned that although the metha-thesis of one halogen^ atom takes place readily, difficulties arise in the exchange of a second, vicinal, halogen atom because the first nitroxy group exerts a negative neighbouring group effect* This effect was clearly demonstrated by Fishbein (16) in the study of the reaction of d,l-and meso-2,3-dibromobutane with silver nitrate in acetonitrile: only the monobromonitroxybutane could be prepared with retention of configuration. The corresponding dinitrate was formed slowly from this with inversion. 0-tosyl compounds have been transformed to nitrate esters via the corresponding iodo compound (17)* Nitrate esters have been prepared by ring-opening reactions of epoxide compounds (I) (III)(V). Depending on the attacking reagent P-hydroxy nitrate (II) (IV) (18) (19) or mixed esters of nitrous and nitric acid (VI) (20) were obtained* Similar additions took place at the olefinic double bond (VII). Addition of dinitrogen tetroxide produced the C_-nitroso nitrate (VIII) (21). With certain metal nitrates in the presence of iodine, instead of the 0-hydroxy nitrate the corresponding {3-iodonitrate was obtained as in the case of cyclohexene (IX) (22). RCH CHR V HNO-s RCH CHR OH T)NO, HNO-: RCH — — CH o \ / * 0 III CH 3 -CH-^H2 V N 2 0 4 RCH -I OH CH2-ONOj IV CH3 -CH-CH2-ONO2 ONO VI CH, X C=CH 2 C H : VII N 2 0 4 CH, CH 3 \ C- C H 2 - 0 N 0 2 3 NO VIII ONO, ON 0-o r IX C H 3-NHN0 2+ H N 0 3 C H 3 - 0 N O 2 4- N20 + H 2 0 XI C 2 H 5 0 H + 0 2 N 0 0 C - C 6 H 5 XII C2.H5NCO +. N 2 O 4 XIII [C2H5N2N03] C 2 H c j-ON0 2 + CgH5C"00H -*• [ C 2 H 5 N 2 N 0 3 ] + C 0 2 XIV C 2 H5 0 N 0 2 + N 2 - 5 6 -Other miscellaneous reactions are also available for the preparation of particular nitrate esters, such as the nitrolysis of N-nitro-methylamine (XI) (23) or the alcoholysis of acylnitrates (XII) (24). Benzoyl nitrate (XII) for such a reaction may be prepared from benzyl mercurychloride according to Titov (25). Nitrate esters have also been prepared from dinitrogentf tetroxide and isocyanates (XIII) via the corresponding diazonium salt (XIV) as reported recently by Bachman and Michalowicz (26). Analysis The analysis of nitrate esters is based usually on a particular property or reaction of the -ONO2 group or on the N content of the substance. The nitrate group has been determined directly by reductometric titration with titanium III solution (27) (28) or by liberation of the nitrogen as N03~ from certain organic nitrates (29) (30) in a suitable reaction and determination of the nitrate anion with nitron (30) or other (31) reagent, or even by electrometric titration (32). Both the Dupont semimicro-nitrometer method (33) (15) and the colorimetric determination by means of transnitrification to 2,4-xylenol (34) (13) are very sensitive and selective for nitrate ester groups. Other colori-metric methods are also available (35) (36) (37) (38). The conventional Dumas micro combustion has limited value because nitrate esters are very explosive, however reasonably good results may be obtained by dilution of the sample with pure glucose (39) (14). Special methods developed recently include determination by non-aqueous titration (40), determination by infrared spectroscopy as applied to nitrocellulose in acetone solution at 11.92yu. (41) and a special modification of the polarographic analysis combined with other methods (42). - 7 -Perhaps the most important method has been the reduction of the nitrate group to ammonia and, after steamdistillation, titrimetric determination of the ammonia in the distillate. The reduction is usually carried out either by use of a special alloy (43) (Devarda alloy) or by the very popular Kjeldahl digestion. The original microKjeldahl procedure was modified for the nitrate esters (44) (45) and improved by several authors (46) (47) (12) (13). A further modification of- this analytical method on an ultramicro scale combined with a Nessler colorimetric ammonia determination was developed in this research and will be discussed later. Spectra Relatively l i t t l e is known about the spectra of nitrate esters. The visible and near ultraviolet spectra are m§rt or less similar to the spectra of the parent compounds. Much more interesting are the infrared spectra of the nitrate esters, however the number of published spectra is very limited. The N02 group in the covalent nitrates has an asymmetric and a symmetric frequency around 1640 and 1260 cm"1 respectively (48). Most of the measurements have been made on explosives such as nitrocellulose (49) (41) and nitroglycerine (50) (51). Systematic studies were made by a few authors such as Bellamy (52) (1650-1610 cm'1 and 1300-1250 cm"1) and Lecomte and Mathieu (53). The most extensive studies were carried out by Brown (54) (1639 + 13 cm 1 and 1279 + 7 cm"1-) and more recently by Hayward (1) who has recorded the infrared spectra of some 23 organic nitrates. Chromatography The chromatography of the nitrate esters has not been developed extensively, . Even Lederer and Lederer have mentioned in their book on chromatography (55) only Ohman's separation (1944) of ethyl, butyl and glycol nitrates by the Tiselius' frontal analytical technique (56). No publications are listed in the Journal of Chromatography concerning organic nitrates in the available first two volumes. However chromato-graphic analysis both on column and paper are extremely important in nitrate ester chemistry. Purification of the crude nitrates in some cases is almost hopeless without column chromatography in view of their explosive pro-perties and paper chromatography is also a powerful tool both as a preparative method and in the study of different nitrate reactions© In this laboratory alumina has been used as a column adsorbent with a suitable solvent (ether or ether-ethylacetate mixture) (12) (13) while for paperchromatographic analysis hexane-methanol (1:1) (12) (13) and petroleum ether (b„p» 67-69°C)-methanol-water (10:4:1) (13) were used as developing agentse For the detection of nitrate esters on chromatograms diphenyl-amine was used either in sulphuric acid solution (57) (12) or in alcohol followed by U.V. irradiation. The latter method was developed ini t i a l l y for the detection of inorganic nitrates (58) and was first applied in this laboratory (13) (59) to organic nitrates. Usually descending chromatography was used but a systematic study of the ascending technique also was carried out by Kitchen (59). - 9 -Reactions The reactions of the nitrate esters are manifold and differ from those of carboxylic esters and aromatic nitro compounds in that, in addition to normal hydrolysis, both hemolytic and heterolytic cleavage of the 0-N02 bond are observed. The subsequent reactions of the fragments formed in the latter reactions are discussed in detail in reviews (1) (2) (3) and in recent theses (12) (13). The reactions with pyridine of different organic polynitrates are well-known from recent publications (7) (8) (9) (45). In Table I are compared the apparent reaction rate constants fear the nitrate-pyridine reaction of the cis and trans-cyclohexane-1.2-diol dinitrates (12) and the three isomeric isohexide dinitrates (13). A l l the reactions were f i r s t order in nitrate ester, but because pyridine was not only reactant but also solvent at the same time its concentration change was negligible and the observed rate constants would include the pyridine concentration: k » k» (pyridine) Apparent activation energies and pre-exponential factors' were calculated from these data for the isohexide dinitrates (13). A similar study of nitrate ester decomposition in solution by Cheeseman has recently appeared (60) (61) (62). Particularly interesting were the reactions of diphenyl methyl nitrate (XV) and 9-Fluorenyl nitrate (XVIII) with piperidine and pyridine respectively according to the following equations. Both reactions took place at room temperature, however no kinetic measurements were reported. - 1 0 -T ABLE I DECOMPOSITION RATE CONSTANTS FOR DINITRATES k(secM )x i o 6 l l5"C I00°C 87°C » isoidide dinitrote 2 5 . 4 8 5 8 3.20 Isosorbide dinitrote* 15 2 2 29 I.i5 isomannide dinitrate g gj Q.74 0.13 trart8-cyclohexone-l,2-diol a . 0 6 dinitrate cis- cyclohexgne-l,2-dioi 4 39 dinitrote «• (13) Calculated from t. values in (12) 1/2 Ph 2CHON0 2 * 2 C^H,, N PhgCHNCgH^ > C 5 H„ N, HNO XV XVI Ph 2 CH-0 -N0 2 • C 5 H n N - Ph 2 CO • . C ^ ^ H N O ^ XV XVII 11 -Acenaphthene Chemistry Structure of Acenaphthene The hydrocarbon C1 2 H10 w a s f i r s t prepared from coal tar by Berthelot in 1867 (63) and the structure vas established by synthesis from naphthalene and acetylene (64) and from 1-ethylnaphthalene (65) by pyrolysis, Berthelot first named the compound acenaphthene probably in reference to its synthesis from acetylene and naphthalenes An extensive investigation started after 1873 when acenaphthene became commercially available in Germany (66), Acenaphthene was isolated from coal tar by distillation (67) and the fraction boiling between 250 - 300° contained the bulk of the acenaphthene. The greatest activity in acenaphthene chemistry was due to Graebe who not only confirmed the formula (68) and structure (69) of acenaphthene but also published a series of papers (69) (70) (71) (72) (73) (74) (75) in which he described the synthesis and characterization of several derivatives. The structure of acenaphthene was established by oxidation, dehydrogenation and finally by synthesis. The proposed structure (XX) satisfied the results of the chemical transformations. The numbering of the carbon atoms of acenaphthene, which is used for a l l the derivatives, was suggested by Sach and Mosebach (76), Obviously structure (XX)cannot be correct, because of the tetrahedral geometry of the carbon atoms. The stereochemical aspect would require a structure in which the two valence8? of the naphthalene nucleus connected to the ethylene group should be bent - 12 -from the normal sp orientation either toward ea>ch other in the plane of the naphthalene nucleus or toward each other but also twisted out of the plane. This uncertainty about the acenaphthene spatial ar-rangement s t i l l exists. The latest publication concerning the interatomic distances of the acenaphthene molecule appeared in 1949 (77) in which the results of X-ray diffraction studies on crystalline acenaphthene were stated as follows: "Acenaphthene crystallizes in space group c£ v =B P cm 2, with four molecules in the unit cell with the measurements a=8.3; b=13.98; c=7.3 A . The structure consists of two layers of molecules which are not bound mutually by symmetry-operations. The line of symmetry of the molecule lies in the plane of symmetry of the crystal. The acenaphthene molecule (XXI) is planar. The distance between CH2 groups is 1.64 + 0,04 A f the width of the benzene ring is 2,355 +.0.01 A* . The dimensions in diagonal direction have been determined with less accuracy, the average value does not differ from generally accepted ones. Increase with respect to normal single C-C bond explains the considerable tension which exists , in the molecule, A decrease of 0.08 A across the width of benzene nucleus is evidently also connected with this strain. A suggestion thus follows that the organic molecule is a considerably more flexible system than hitherto believed. The normal distance for single, double, etc. bonds appears to occur only in the unstrained simple structures. In addition, i t is necessary to mention that the structure of naphthalene established with respect to the inter-atomic distances is completely inaccurate. It is known that in naphthalene itself the benzene nuclei to a f i r s t approximation can be considered as a regular hexagons with 1,4 A* sides. However the nature of this distortion has not , as yet been experimentally established." Certain calculations from these data are discussed in the section of Results and Discussion, - 13 Reactions of Acenaphthene Host of the classical reactions of acenaphthene were reviewed in detail by Hahn and Holmes (78) therefore mainly more recent publications will be mentioned here, Hydrogenation was fir s t studied by Sabattier (79) in 1901. At elevated temperature and pressure destructive hydrogenation takes place (80). From acenaphthene at 450-470°C was produced, under 70 atm. hydrogen pressure with alumina or a mixture of aluminum, iron and copper oxide catalyst, naphthalene and hydrocarbon mixtures (b8p. 80-200°C). It seems to be general from several publications that in the f i r s t stage of "oxidation", dehydrogenation takes place to produce the fully conjugated acenaphthylene (XXII). The acenaphthene undergoes oxidation by different routes which depend mainly on the reaction condition^ although in some cases polymerization also takes place. The first experiments on acenaphthene oxidation were due to Graebe (70) (71) (72)« Oxidation with chromic oxide in acetic acid yielded acenaphthenequinone (XXIII) while potassium permanganate produced naphthalic acid (XXIV). A powerful chromic acid oxidation yielded naphthalic anhydride. The process developed by Graebe gave a 40% yield of acenaphthenequinone and the oxidation to naphthalic acid was almost quantitative. It should be mentioned that the oxidation of acenaphthene is not simple, either in theory or in practice. The oxidation proceeds probably via a large number of intermediate stages and among the inter-mediates are not only simple acenaphthene derivatives, but also dimer ketones such as biacenaphthylidene ketone (XXV) and biacenaphthylidene difeetone (XXVI). -14-XXVI Z : 0 - 15 -This is a clear indication that the yield and purity of the synthesized acenaphthenequinone depend very much on the reaction conditions. Russian authors (81) (82) also published methods for acenaphthene oxidation with chromic acids. Calcium permanganate was suggested by Morgan (83) as a suitable oxidizing agent. The patent literature of the contact catalytic oxidation of acenaphthene is very voluminous, and among the several dozens of publications only one will be mentioned, Jager described (84) in one of his patents an oxidation method which employed air and an alkali tie. or alkali^ earth metal catalyst. The ratio of the products varied with the acenaphthene to air ratio and with the temperature. At the concentration of 1 to 1.5 g of acenaphthene (XXI) to 5-30 1 of air at 310-330*C mainly acenaphthylene (XXII), acenaphthenequinone (XXIII) and the dtfcetone (XXVI) were produced. If the concentration was low such as 1 g of acenaphthene to 30-200 1 of air and the temperature was raised to 330-360°C naphthalic acid (XXVII) was produced in good yield* Recently Sasayama (85) reported catalytic oxidation of acenaphthene in the vapour phase at 400°C over vanadium pentoxide catalyst. Among the different products phthalic anhydride was identified. Another oxidative method reported by Monti employed selenium dioxide. Without solvent (86) in the molten state acenaphthene produced acenaphthylene (XXII) (25%) and a mixture of the cis-(XXIX)-and trans-(XXX)-acenaphthene-l,2-diols (16%). In acetic acid (87) solution the reaction was more complex. In addition to the diols and acenaphthylene, -16-XXVII XXVIII f XXIX XXX X X X i - 17 -polymerised acenaphthylene and dinaphthylene cyclobutane (XXXI) were formed,, The latter compound is stereochemical^ interesting. If one considers that acenaphthene is planar and the four hydrogen atoms on and of the acenaphthene are out of the plane of the rings then i t is probable that the two acenaphthene nuclei in( XXXD would enclose an angle of uncertain but fixed magnitude, Monti also reported (87) that oxidation of acenaphthene with lead tetraacetate in acetic acid solution at room temperature produced only acenaphthylene (XXII) at 100-110°C, A l l the above-mentioned products were formed except the acenaphthene diols. Although procedures were published for the preparation of haloacenaphthenes in the last century the fi r s t really pure sample (5-bromo-acenaphthene) was prepared in 1903 by Graebe (75), From the 5-amino acenaphthene Sachs and Mosebach (88) prepared the corresponding chloro, bromo and iodo derivatives. Direct bromination and chlorination took place on the five-membered ring in carbon tetrachloride solution i f the reaction mixture was exposed to bright sunshine. By this photo-chemical halogenation Jc\nes (89) prepared both the 1-mono- and 1,2-dihalo-acenaphthene, Greene(90) reported bromination of acenaphthene by means of N-bromosuccinimide, The crude product was a mixture of two dibromo derivatives, the yield of 1,2-dibromoacenaphthene was approximately 8 times greater than that of the l,5(?)-dibromoacenaphthene0 Nitration of acenaphthene was studied first by Quincke (91) (92), His results were confirmed by Briones (93) and Graebe (75), Acenaphthene on treatment with concentrated nitric and sulfuric acid - 18 -mixture produced two nitro derivatives, one of which was nitrated at the position 5, the other was dinitrated at the 5 and 6 carbon atoms, Jamazaki pointed out in recent publications (94) (95) that,while mixed acid yielded the 5,6-dinitroacenaphthene, nitration in glacial acetic acid produced a mixture of 3,6-dinitroacenaphthene and 3,8(?)-dinitroacenaphthene. The ratio of the two products was shifted toward the 3,6-isomer with increasing nitric acid concentration. The nitro derivatives could be oxidized either to nitro naphthalic acid or to the corresponding nitro acenaphthenequinone?,, The 5-mononitro and 5,6-dinitroacenaphthenequinones were also synthesized (96) by direct nitration of the acenaphthenequinone. The nitro groups could be reduced to amino groups to yield the corresponding amino acenaphthene derivatives. The preparation of the amino-nitro acenaphthene derivatives usually requires some indirect method. An excellent example was the synthesis of the 5-amino-6-nitro acenaphthene prepared fi r s t by Richter (97) in 1956* He started from acenaphthene (XXI) and by Friedl-Craft's reaction ob-tained the 5-acetyl-acenaphthene (XXXII), previously prepared by Nightingale and coworkers (98), After nitration (at the 6 position) the oxime (XXXIV) was prepared which underwent a Beckmarm-type re-arrangement to form the N-acetyl-5-amino-6-nitro-acenaphthene (XXXV) from which by hydrolysis the corresponding 5-amino-6-nitro-acenaphthene was liberated, Acenaphthene is sulfonated with concentrated sulfuric acid and different isomers may be isolated according to the reaction conditions. -19-'1 XXXVIII XXXIX - 20 The orientation of the sulfonyl group was undecided for a long time after the first syntheses,, It was a nrni-SRleading fact that both the 3- and 5-sulfonated acenaphthene formed acenaphthylene (XXII) on alkali fusion. That was the reason why earlier workers (99) stated that the sulphonyl derivative was the acenaphthene-l-sulfonic acid. Because the 3- and 5-hydroxyl acenaphthenes are relatively stable Johnes assumed in his historical review (89) that the sulfonyl group probably migrated to the 1-position and the acenaphthene-l-ol formed in the alkali fusion dehydrated to acenaphthylene. Derivatives of Acenaphthene Some of the acenaphthene derivatives were mentioned above, here only the most important will be discussed. Acenaphthylene is a fully-conjugated unsaturated molecule (XXII). It is obtained on the dehydrogenation of acenaphthene in the vapour phase in an empty, redhot quartz tube (100) or over catalysts such as elemental carbon or silicon (101) or mixed metal oxides (89) (around 500-650°C). Some of the procedures connected the dehydration with oxidation using air or other oxygen-bearing gas over oxides such as manganese oxide at about 400°C (102), According to Campbell (103) acenaphthylene and its polymer were also formed during the manufacture of carbon black from natural gas. As was mentioned before, alkali fusion of sulfonated acenaphthene (89) also produced acenaph-thylene. Other methods include photochemical synthesis from ace-naphthene (104) as well as thermal decomposition of 1-acetoxyacenaphthene (105) and acenaphthene oxidation by N-brorao-succinimide (106), - 21 -Acenaphthylene is an orange colored crystalline compound melting at 92 - 93°C. It readily absorbs bromine with the formation of 1,2-dibromoacenaphthene. Hypochloric acid addition instead of the J expected chlorohydrin yielded (107) a mixture of the cis- and trans-1,2-dichloroacenaphthene. Acenaphthylene is easily polymerized to polyacenaphthylene and oxidized to naphthalic acid, Acenaphthenone (XXXIX) was synthesized fi r s t by Graebe and Jequier (73) and later by Marquis (108). An indirect synthesis was described by Fieser and Cason (109) via the monohydroxyl acenaph-thene (XXXVIII) (110), This steam volatile mono-ketone (XXXIX) is a colourless crystalline compound with a melting point of 121°C, Acenaphthenequinone may be prepared either by oxidation of acenaphthene as discussed above or by hydrolysis of its dioxime which may be synthetized directly from acenaphthene by means of amyl nitrile (111). Acenaphthene-quinone (XXIII) is a yellow, crystalline compound. The reported melting points differ, the most accepted value is 261°C given in several handbooks. Actually the compound is a 1,2-difcetone but since from its first synthesis i t was considered as a "quinone" i t is commonly known by that name. Recently a true ortho-quinone of acenaphthene, i.e. 4,5-acenaphthenequinonediimide was synthesized by Weberg (112). Similar reactions take place in the naphthalene nucleus of acenaphthenequinone as in other kinds of acenaphthene derivatives, but the most characteristic reactions involve the carbonyl groups. 22 -These may be classified roughly in three groups. (1) Addition and replacement reactions ranging from Grignard addition to the action of phosphoruspentachloride, (2) Condensation reactions in-cluding amino-oxo condensations and condensation with benzene in the presence of aluminum chloride, and finally (3) Oxidation-reduction reactions including oxidations to naphtaldehydic and naphthalic acids and reductions by different methods to the corresponding mono-ketone or to the diols. Acenaphthene-1,2-diols frequently are called acynaph-thylene glycols (from the resemblance to ethylene glycol). Two stereo-isomers are possible, the cis- and trans-acenaphthene-1.2-diols. The trans-isomer has two identical asymmetric centres and as usually synthesized is the 1:1 mixture of the D-and L-forms that is the racemic form. The >'s cis- isomer therefore stay: beAconsidered a meso- form. Theoretically the compounds could be synthetized in several different ways, but practically the most important is the reduction of the acenaphthenequinone. Jack and Rule (113) hydrogenated acenaphthene-quinone in alcohol solution in the presence of platinum catalyst and ob-tained cis- and trans- acenaphthene-1,2-diol in yields of 26.8 and 23.7% respectively. It is interesting that in the lithium aluminum hydride reduction the ratio of the isomers was quite different as reported by Trevoy and Brown (114), The latter authors reported yields of 157. cis- and 457. trans- which indicated a different stereospecifity of the two methods. Other preparative methods were also available such as direct oxidation of acenaphthene with selenium dioxide (86) (87) or the reaction of acenaphthylene with osmium tetroxide (115) which - 23 -produced only the cis-isomer. The hydrolysis of the corresponding dihalocompounds was among the first methods developed but today is used only for the identification of different halogen acenaphthene derivatives (107). Several polycyclic compounds containing the acenaph-thene skeleton are described in the recent literature. One of the simplest compounds aceanthrane (XL) contains a benzene ring fused to the naphthalene nucleus (116). Another contains a benzene ring fused to the five-member ed ring (f luoranthrene XLI). The combina-tion of the two types of structure occurs in 2:3-benzofluoranthrene (XLII)(117). Another type of structure has two acenaphthene units fused to one benzene ring (XLIII)(118). Carcinogenic compounds were obtained (119) when nitrogen-containing heterocyclic rings or ring systems were attached to the fluoranthrene (XLI) molecule. Other structural types have five- and seven-membered rings attached to the acenaphthene nucleus at similar positions to that of the first five-membered ring. Pyracene (XLIV) may be partly or fully unsaturated giving respectively 1,2-dihydropyracylene (XLV) and pyracylene (XLVI) (120). Similar .to acenaphthenequinone is the corresponding 1,2-diketopyracene (XLVII) (121) which is not named "pyracenequinone". Acepleiadiene (XLVIII) contains an unsaturated seven-membered ring in the same position (122), -24-XL XLI XLII XLVil XLVIII - 25 -RESULTS AND DISCUSSION - 2 6 -In the present work the molecular dimensions of acenaph-thene were derived from the X-ray data of Kitaigorodskii ( H ) by a simple series of calculations (Appendix 1) based on the following assumptions: (1) Suppose the CH2 distance from the naphthalene nucleus to be the average aliphatic-aromatic C-C distance (as in toluene) 1.52 I (123). (2) Suppose that the distortion of the naphthalene nucleus (a decrease of approximately 0,1 A on the longest axis of the naphthalene molecule) to be due entirely to the distortions of the angles while the C-C distances remain the same as they are in the naphthalene molecule (123) (124) (125) (126) (127). The degree of distortion is illustrated in Figure 1 where a normal naphthalene molecule and a planar cyclopentane ring drawn to scale were placed in contact. The cyclopentane ring has the dimensions required for acenaphthene according to the measured (77) and assumed values. According to the calculation both positive and negative angular distortions (which are never greater than 5.5°) take place, with certain angles remaining unchanged. The sum of the calculated internal angles of the hexagons are shown in Table II together with the theoretical and observed values for naphthalene. The discrepancy indicates the degree of error in the calculation. Using the calculated angles and assumed interatomic distances the acenaphthene skeleton was constructed (Figure 2). The molecule could not be built up from commercially available atom models. Using the atomic radii (Table III) according to Stuart (128) and - 27 -1.64 I' 2' 4 120° 5 0 ' 121° 5' I! 9° 3 5 ' 118° 55' 120* 10' ! I9°30' ir-I V s V» b< c 122* 17" 124* 0' !I4* 9' 121 • 51' 120*10' 116*54' 117* 2 0* 105* II* 106*9* Figure 1 The Carbon Skeleton of Acenaphthene - 28 -Table II Sum of the Internal Angles of the Hexagons in the Acenaphthene Molecule Theoretical Observed in Naphthalene Calculated for Ac enaphthene 720°00* 720°05* 719°21* Table III Atomic Radii Atom Radii (A)* Aliphatic carbon Aromatic carbon Hydrogen Oxygen 1.27 1.27^ 1.61 ff 1.00 1.27 *) According to Stuart (131) and Briegleb (132) - 29 -Figure 2 Bond Lengths of Acenaphthene - 30 -Briegleb (129) which were used in the manufacture of Calotte models (E, Leybold's Nachfolger, Cologne, West Germany (130)) the picture of the molecule shown in Figure 3 was obtained. It seems clear that 5-membered ring in acenaphthene is planar and the hydrogen atoms on C^  and C 2 are fully eclipsed. In trans-1.2-derivatives. therefore, a single staggered conformation of the substituent groups is fixed by the ring system. Commercial acenaphthene after careful purification had the correct physical constants according to the reported values. Both the infrared and ultraviolet spectra were recorded. The characteristic absorption bands in the infrared spectrum are identi-fied in Table IV, Oxidation of acenaphthene to the corresponding 1,2-diketone (acenaphthenequinone) was carried out in glacial acetic acidssolution with sodium dichromate according to the procedure given in Organic Syntheses (131), It was found that the yield of crude diketone could be considerably increased over the reported values (42-60%)by repeating the "bisulfite extractions", Acenaphthenequinone was also obtained by careful puri-fication of crude samples obtained from Eastman-Kodak Company, This material then gave the correct analytical values for carbon and hydrogen. - 31 -Figure 3 Molecular Model of Acenaphthene - 32 -Table IV Principal Infrared Absorption Bands of Acenaphthene Frequency (cm-1) Intensity Explanation 3080 2930 1605 1595 1425 1370 895 840 785 745 weak weak strong strong medium strong weak strong strong weak arom. C-H stretch, alycyclic C-H stretch, arom. ring vib. arom. C-H bend alycyclic C-H bend cyclopentane ring vib. Table V Melting Points and Carbonyl Frequencies of Acenaphthenequinone Synthetic Quinone Purified E.K. Quinone Reported Values Ref. Highest m.p. Infrared Carbonyl Frequency (cm ) 264 - 266°C 1770 1718 273 - 274°C 1718 261°C 1776 1736 (134) (135) - 33 A comparison is shown in Table V of the melting points and infrared carbonyl frequencies of the synthetic and purified commercial acenaphthenequinone together with the reported valuese The solid material removed from the Eastman-Kodak sample by ether extraction melted at 247 - 253° after repeated recrystallIzation and the infrared spectrum of this unidentified product showed not only the moan peak at 1718 cm"1 but also another intense peak at 1770 cm"1. Similar results were obtained with the impurities removed from the synthetic acenaphthenequinone. The presence of this impurity in the crude acenaphthenequinone preparations could also be detected by com-paring the spectra of the crude and pure products. The spectra were very similar but a few extra peaks could be observed in the spectrum of the impure quinone (Appendix 2, Spectra 2, 3 and 4). The above evidence indicated that in the oxidation of acenaphthene, among the several by-products there is one or more compounds having a similar structure and similar physical properties to acenaphthenequinone0 It seems probable also that the measurements of Josien and Fuson were made on impure quinone and that the pure quinone has a single carbonyl frequency at or near 1718 cm ^. The ultraviolet spectrum of the pure acenaphthenequinone was also recorded (Appendix 3, Spectrum 2). Paper chromatographic examination (solvent C) showed that a fresh solution of pure acenaphthenequinone gave only one brown ab-sorbing spot (RF=0.894 + 0,008) under the ultraviolet lamp. On the other hand acenaphthenequinone in glacial acetic acid solution (8,0x10 after standing a few days at room temperature partially decomposed and - 35 -cjU-isomer (long colourless needles) had a lower solubility than the trans-diol (creamy plates) in the usual organic solvents and in water0 Carbon and hydrogen analyses agreed with the theoretical values for both isomers* The ultraviolet spectra of the cis- and trans- diols were similar to that of acenaphthene and to each other* The spectrum of the trans-isomer, however, displayed shoulders on the principal ab-sorption band for acenaphthene which, in the spectrum of the cis-isomer were clearly distinguished as separate peaks (Appendix 3, Spectra 3 and 4)* The infrared spectra of the diols also were recorded (potassium bromide windows), the characteristic absorption bands of the isomers are listed (Appendix 2). The carbonyl stretching frequency (1718 cm"1) of the quinone was absent while new peaks appeared at the usual OH stretching frequencies. g&SMSie "Ehe two hydroxyl groups are in vicinal position Athe dis-tance between them in the cis-diol is such that intramolecular hydrogen Uv bonding takes place whereas^the trans-diol fchowa only intermolecular hydrogen bonds^ This phenomenon was described recently by Kuhn and coworkers at the 134th meeting of the American Chemical Society (135). Unfortunately the actual absorption frequencies were not reported but only the separation ( A>? = 39 cm 1) between the two OH bands. The numerical values obtained in this laboratory were not directly comparable with the results published by Kuhn et a l . since they used lithium fluoride optics (136) and diluted carbon-tetrachloride solutions of the diols (to avoid inter-molecular hydrogen bonding), whereas, in the present work sodium chloride optics and the crystalline did.Is were - 34 -another, yellow spot with a lower RF value (0.175 + 0.025) appeared on the chromatogram. If pure acenaphthenequinone was left for several weeks in contact with methanol at room temperature i t slowly dissolved (5 x 10 M or less) and lost its yellow colour. A paper chromatogramm of the solution showed several fluorescent spots. After evaporation of the colourless-solution, the residue was again yellow. The hydrogenation of acenaphthenequinone to cis- and trans-acenaphthene-1,2-diols according to the procedure of Jack and Rule (113) was not successful, possibly because the highly active platinum catalyst dehydrogenated the diols formed back to the quinone during the isolation procedure. Reduction with lithium aluminium hydride was fi r s t reported by Trevoy and Brown (114), but without experimental details. The re-ported yields of 15 and 45% for the cis- and trans-diols respectively could not be reproduced; the highest yields obtained in the present work were 1404 and 38.4% respectively. The low yields were largely due to losses in recrystalllzation since the average yield of the crude mixture was 79%. Enzymatic reduction (134) of the quinone was suc-cessful but gave lower yields of the diols than the lithium aluminium hydride method and was more tedious0 Sodium borohydride reduction was not tried, but theoretically i t would be expected to have an advantage in the reduction of nitro derivatives of acenaphthenequinone to the corresponding nitrodiols. The isomeric acenaphthene-1,2-diols were satisfactorily separated and purified by recrystalllzation from methanol. The - 36 employed. For this reason potassium bromide windows were also pre-pared with crystalline cis- and trans-eyelohexane-1.2-diols and the spectra were recorded for a further comparison. The results from the two methods are shown in Table VI together with the values for the cyclopentane-1,2-diols, It was concluded that in the solid state the cis-1.2-diol contains intramolecular hydrogen bonds in addition to the intermolecular bonds which are also present in the solid trans-diol. The diacetates and dibenzoates of the acenaphthene-1,2-diols were prepared and obtained in crystalline form except for the trans-diacetate which was a viscous syrup. The ultraviolet spectra of these compounds resembled the spectrum of acenaphthene, however the maxima in the case of the diacetates were more distinct than for the dibenzoates, The infrared spectra also were recorded (Appendix 2, Spectra 9, 10, 11 and 12), The disappearance of the OH stretching frequency indicated that the corresponding acenaphthene diol was fully esterified. Two carbonyl peaks appeared in the infrared spectra of the dibenzoates while in the spectra of the diacetates splitting was not detected. The separation between the two peaks were 20 and 10 cm"* for the cls-and trans- isomers respectively. It also should be noted that the two peaks in the cis- dibenzoate were approximately the same in intensity while in the case of the trans- dibenzoate the peak with lower frequency was the more pronounced. It is suggested that these differences might arise from the carbonyl-carbonyl interactions but i t is recognized that further data from spectra in dilute solutions would be required to support this hypothesis. - 37 -Table VI Hydroxyl Stretching Frequencies of Cyclic-1,2-diols In CC14 Solution (a) In Solid KBr (b) 1,2-Diol isomer Frequency (cm~l) Free Bonded Free Bonded OH OH OH OH  cis- 3633 3572 61 -Cyclopentane trans- 3620 - 0 -cis- 3626 3588 38 3466* 325^ 150 Cyclohexane trans- 3633 3600 33 3390^ - 0 cis- 39 3330 3190 140 Acenaphthene trans- 0 3260 - 0 (a) From references (135) and (137) (b) From this work (c) From a sample prepared in this laboratory by Hr. A, Zane (12) 38 -The C-O-C frequencies in these compounds appeared to be made up of several superposed bands around 1200 cm*. Jones and Sandorfy (138) pointed out an inverse relationship between the C=rO and C-0-?C (ester) stretching frequencies of the same compound. In a series of different steroid acetates with different degrees of unsaturation the observed frequencies lay on a straight line to a rough approximation. A plot of the observed C-O-C frequencies of the acenaphthene-1,2-diol diacetates and dibenzoates against an inverse scale of the corresponding C=0 frequencies (Figure 4) did not give the same straight line (dotted line) obtained by Jones and Sandorfy, but did establish another linear relationship (solid line). Where splitting occurred the frequency used in the plot was that of the most intense peak which usually also had the lower frequency. Conjugation of the phenyl rings with the carbonyl groups in the dibenzoates induced a lowering of the C=0 stretching frequency and an increase in the C-O-C frequency relative to those of the diacetates as found by Jones and Sandorfy. The frequency shifts were very similar for the cis- and trans- isomers but the difference in the C=0 to C-O-C frequency ratios for the two isomers remains unexplained. Similar differences in the steroid acetates were correlated by Jones and Sandorfy with the degree of unsaturation of the alcohol but this effect is not involved in the present case. It was found possible to prepare crystalline cyclic derivatives (carbonate and isopropylidene acetal) of the cis-acenaphthene-1,2-diol. The carbon and hydrogen analyses of these derivatives agreed with the theoretical values based on the molecular formulae. The absence of cm" 1760 1750 1740 1730 1720 1710 1700 1690 _ J I I I I I _ J L _ - 40 -the hydroxyl stretching frequency in the infrared spectra of these compounds was also evidence of their constitution (Appendix 2, Spectra 7 and 8), The reaction of phosgene with trans-acenaphthene-1.2-diol. on the other hand, produced a brown o i l in approximately the same yield as the carbonate from the cis-diol. Paper chromatography of the o i l showed several spots, however no evidence could be obtained that one of these represented the trans-carbonate. Although i t is fre-quently stated in the literature that only cis- vicinal diols in cyclohexane or cyclohexene rings will form cyclic acetals (139) (140), the preparation of the cyclic acetone compound of trans-cyclohexane-1,2-diol was reported by Christian, Gogek and Purves in 1951 (141). The method used involved azeotropic distillation of the water formed in the reaction (142) and the trans-diol required a much longer reaction time than the cis-isomer. This result could be explained by the energy barrier to interconversion of the two con-formational isomers of trans-cyclohexane-1.2-diol where in the equatorial-equatorial conformer the two oxygen atoms are separated by the same distance as in the cis-(axial-equatorial) isomer (141) (XLIX). Eleven years earlier Petrov (143) described a compound formed from acetone and cyclohexane-1,2-epoxide (L) in the presence of borontrifluoride catalyst as 2,2-dimethyl-hexahydro-l,3-benzodioxole (LI). The physical constants of Petrov1s compound together with those of the cis- and trans- isopropylidene cyclohexane-1,2-diol derivatives - 41 -are shown in Table VII 6 It appears that Petrov's compound was the cis-derivative. Since only the staggered conformation of trans-acenaphthene-1,2-diol can exist the preparation of the cyclic isopropylidene acetal (acetone) derivative was attempted by the method successfully used with the cis-diol. The progress of the reaction could be followed by addition of petroleum ether (b.p. 30-60°C) to the reaction mixture which caused the preci-pitation of unreacted diol. A reaction time of 4 to 12 hours was sufficient to cause complete solution of the cis-diol whereas a much longer time was required for the trans -isomer. The results of two experiments with the trans-diol are summarized in Table VIII 0 In the first experiment a small amount of unidentified solid product (m0p„ 36-37°C) was isolated together with some unreacted trans-diol (m.p. 150 - 153°C). In the second experiment with a much longer reaction time, two different solid products were obtained. One of these was an unidentified, colorless crystalline compound with the unusually high melting point of 343 - 344°C. The other product was cis -acenaphthene-1,2-diol, with the correct melting point of 212-214* and an infrared spectrum identical to that of authentic cis-dlol. This surprising result raised at least two further questions. The first was the mechanism of the transformation from trans- to cis- diol. One could suppose a transition state between the trans- and cis- diol which might be some sort of tosyl ester - 42 -H B V 3 0 / " ^ 3 Table VII Isopropylidene Derivatives of Cis- and Trans-Cyclohexane-1.2-diol Physical constant trans-Acetone Compound prepared cis-Acetone Compound (141) by Petrov (143) Compound (144) Boiling point 77-78°/20 mm - 78°/24 mm 182-183°/760 mm 182°/760 mm Density 04° 0.9787 d|° 0.9803 d|° 0.980 A5 0.9849 on on Refractive Index nj5 1.4468 ng u 1.4489 n1,5 1.4510 H e n i0 1.4479 Obtained 42.65 42.68 M* R* Calculated 42.66 42.65 Table VIII c e •H U 0) P* w Acetonation of Trans-Acenaphthene-1,2-diol Reaction Components trans-Acenaphthene--1,2-diol S •w * 4J W /-> J? C 00 o u OS WW *J U « (0 U 0) m: g. mM m.p.(°C) mg. Products Pet. ether soluble fraction mg. m.p.M Benzine soluble fraction mg. m.p.(«c) 187 1 157.5-158.5 3 77 56 36-37° 85 150-153° 3723 20 157.5-158.5°90 1250 10 212-214' 30 343-344° 0 Hydrated p-toluene sulfonic acid (p-CH3CgH^S03H.H20) - 43 -(for example a semi-tosylate). This hypothesis might be tested by reacting different tosyl esters of acenaphthene-1,2-diols with acetone under similar conditions. The other question was the mechanism of the for-mation of the acetone compound in the case of the cis-diol. To resolve these problems further experimental work will be required. It was concluded from the above experiments that the cyclic acetal of the trans-diol may have been formed in low yield, but that competing reactions of inversion and decomposition (and possibly polymerization) also occurred. The preparation of the dinitrate esters of the diols was carried out in nitric acid (100%) - acetic acid - acetic anhydride. The ratios of the reagents, the yields, nitrogen contents and physical constants of the products from both the cis- and trans-acenaphthene-1,2-diol are shown in Table IX. The dinitrates were colourless crystalline compounds which were stable in the dry state. When absorbed on aluminium columns they were slowly decomposed by light. After standing for a absolute few days in &bs«&H*?& dry acetone or^methanol solution at room tempera-ture a slight decomposition was detected by paper chromatography. The Rp values of the dinitrates in different solvent systems are shown in Appendix 4 . The ultraviolet spectra of the dinitrates (Appendix 3) showed a close similarity to the parent diols as well as to acenaphthene. The dinitrates had max values identical to those of the corresponding - 44 -Table IX Nitration of cis- and trans-Acenaphthene-1.2-diols Reagents Products N% Isomer Diol HN03 mM ACOH mM AC20 mM 8 . , £ Crude! Final min % \"L max.m.p. Found Calcd. cis- 1.0 218.0- 4.0 3.3 20.0 100 94.2 12.9 128.0- 9.93 10.15 219.5° 130.5° trans- 1.0 160.0-163.0 4.0 3.3 20.0 35 92.4 16.6 98.5- 10.17 10.15 99.5° Table X RF Values of Products from the Reaction of Pyridine with Cis- and Trans-Acenaphthene-1,2-diol Dinitrates Average Rp Values* Cis Trans 0.963 ± 0.005 0.960 + 0.009 0.899 + 0.013 0.910 + 0.008 0.513 + 0.013 0.127 + 0.005 Undecomposed dinitrate Unknown No. 1 Unknown No. 2 Unknown No. 3 *> Each value is the average of 20-24 separations - 45 -diols. The infrared spectra also were recorded (Appendix 2) and the absence of hydroxyl peaks and the presence of the characteristic covaient nitrate frequencies around 1265 and 1650 cm"* supported the assigned structure (1) (52). Further evidence was provided by hydrogenation of the cis- and trans-acenaphthene-diol dinitrates. The recovered diols had the correct melting points and mixed melting points and infrared spectra identical to those of the standard diols. Reduction of the nitrate esters with lithium aluminium hydride or with sodium borohydride was not clean-cut. Paper chromatography showed up spots resembling the parent diols but because of the large amounts of by-products the pure diols could not be isolated. Both cis- and trans- acenaphthene diol dinitrates were reacted with boiling anhydrous pyridine in the manner of pre-vious experiments (12) (13), Nitrogen oxide evolution was not observed, but the solution turned dark yellow after a short time. The progress of the reaction was followed by paper chromatography. After a rela-tively short period (0,5 hours) the paper chromatogram indicated that a l l the nitrate ester had decomposed and acenaphthenequinone was formed. After further refluxing the acenaphthenequinone also decomposed and produced unidentified spots on the paper chroma-togram. After refluxing for 25 hours the quinone had almost com-pletely disappeared. - 46 -Another experiment carried out at -20°C indicated that after 25 hours the nitrate ester had also partly decomposed. After acidi-fication of the reaction mixture nitrous acid was detected by a spot test using aqueous safranine solution according to Carbon! (145). These experiments indicated that both of the cis- and trans-acenaphthene-1,2-diol dinitrates were decomposed by pyridine and from both isomers acenaphthenequinone and nitrous acid were formed. In a kinetic study at 25.2 + 0.1°C pyridine solutions of the cis- and trans- acenaphthenedioldinitrates (initial concentrations 0.101 + 0.001 and 0.102 + 0.001 molar respectively) were analysed at the intervals from 1 to 900 minutes. The ether-soluble reaction products were separated on paper chromatograms and the quantity of unreacted dinitrate was determined directly from the developed chromatogram by 17.V. spectrophotometry. The average Rp values of the reaction products are shown in Table X. Unfortunately in the most suitable solvent system (solvent C) one of the unidentified products travelled with the acenaphthenequinone and the appearance of the latter could not be determined quantitatively. At t'Q (65 seconds) the concentration of trans -dinitrate was 0.101 molar indicating that practically no decomposition had occurred. The logarithm of the concentration of unreacted dinitrate (Table XI) when plotted against time gave a straight line indicating a first order reaction (Figure 5), The order of the reactions was determined numerically from a plot of the logarithms of the actual reaction rates against the cor-responding concentrations (Table XII). - 48 -Table XI The Rate of Reaction of cis- and trans-Acenaphthene-1.2-diol Dinitrates With Anhydrous Pyridine at 25.2 + 0.1°C Dinitrate concentration g M/1 TIME 10.5 30.0 90.0 180.0 270.0 300.0 637.0 900.5 (min.) 0.97 0.096 0.092 - 0.076 - 00490 0.P350 0.081 0.078 0.044 0.026 - 0.011 cis-trans -Table XII Rate Constants for the Decomposition of Acenaphthenediol Dinitrates In Pyridine at 25.2 + 0.1°C Calc'd. k x 106 Standard Isomer Order (sec"*) Deviation cis 1.07 19.0 + 1.7% trans 0.97 123 + 12% - 49 -The first order rate constants were calculated and from the percentage deviations of the observed values from the straight line the standard deviations were determined (Table XII). A comparison of these apparent rate constants with those in Table I measured for other dinitrates in boiling pyridine (115°) showed that the decomposition of the acenaphthene-1,2-diol dinitrates in pyridine was much faster. This difference may indicate another mechanism in the nitrate ester-pyridine reaction. It also should be noted that although side reactions appeared to occur, particularly in the case of the cis- acenaphthene-1,2-diol dinitrate, the main route of the reaction seems to be common for the a two isomers withAcommon intermediate which s t i l l contained a nitrate ester group (diphenylamine test). The reaction resembled the de-composition of 9-nitroxy fluorene (XVIII) in pyridine (61) however the mechanism of both reactions are s t i l l unknown. For a l l the experiments discussed above pure cis- and trans-acenaphthene-1.2-diols were used. These diols were obtained from carefully purified Eastman-Kodak acenaphthenequinone by lithium aluminium hydride reductione The purity of the diols depended very much on the purity of the acenaphthenequinone used. If the quinone was not pure the cis- and trans-acenaphthene-diols obtained had low melting points which could not be increased by as many as five recrystallizations. Although paper chromatography showed only single spots for each isomer, the infrared spectra of the impure diols showed a l l the peaks of the pure substances plus additional peaks. In the case of the impure - 50 -cis-diol only some of the peaks showed small shifts in frequency (Appendix 2). Purification of these diols by absorption or partition chromatography or by sublimation- at 0,001 mm pressure were unsuc-cessful as judged by the melting points. The melting points of the diacetates, dibenzoates, and dinitrates of the impure diols also were different from those of the same derivatives prepared from the pure diols even after several steps of column chromato-graphy and recrystallization. (Table XIII). - 51 -Table XIII Melting Points of Pure and Impure Acenaphthene-1,2-diols and Their Derivatives cis-Acenaphthene-1,2- trans-Acenaphthene-1,2-diol diol pure impure pure impure Diol 218.0-219.5° 153-159° 162.5-163.0° 132-158° Diacetate 134.5-136.5° 61-70° o i l Dibenzoate 148.0-149.5° 113.5-115.0°C 148.0-149.5? Di-3,5-dinitrobenzoate 93-130° Dinitrate 126.0-127.5° 122.0-124.5° 98.5-99.5° 104.0-110.0°C - 52 -Suggestions f o r Further Work - 53 -1. ) The intramolecular hydrogen bonding in acenaphthene-1,2-derivatIves should be investigated by infrared and nuclear magnetic resonance spectroscopy in dilute solution in suitable solvents. Since the separation of oxygen or nitrogen atoms at and C 2 is established by the fixed conformations of the mole-cules, the relationship between the length and the strength of such bonds could be determined. 2. ) Steric factors in replacement reactions at and C 2 of the acenaphthene structure could be assessed by comparison of rates and relative activation energies for the isomers. 3. ) The relationship of the C-O-C and C=C frequencies in organic acid esters of the cis- and trans- acenaphthene-1,2-diols in suitable solvents should be extended. 4. ) After further study of the reaction products the true rate con-stant (and order) of the pyridine-nitrate reaction might be determined by controlling the concentration of pyridine in •>. - 54 -the reaction in a solvent such as benzene. Relative activation energies for the isomers should also be established by this method. These nitrate esters might be suitable substrates for an investigation of photolytic cleavage of the O-NO2 bond and the steric factors in such free radical mechanisms. This type of investigation might be extended to other mole-cules containing five-membered carbocyclic or heterocyclic rings in fused systems. The fluorene and acenaphthene derivatives discussed here may be regarded as early members of such a series of compounds. - 55 -E X P E R I M E N T A L - 56 -A) MATERIALS 1) Acenaphthene "Practical" grade (95%) Eastman-Kodak acenaphthene was distilled in vacuo through a 22 cm Vigreaux column into a sausage-shaped glass receiver which was cooled in dry-ice-acetone (Figure 7) . The observed boiling point was correct at 109-113°C at 4-6 mm falling within the rectangle on the Cox diagram,Figure 6, which was con-structed from reported values of vapour pressure and temperature (146), The white solid distillate (yield 79,5%) was recrystallized from 5 parts of 95% alcohol after treatment with charcoal. The over-a l l yield was 66*6% of colourless product melting at 96,0-96,5°C, The reported m.p, was 96.0°C (146), The picrate melted at 165.5-166.0°C and the reported m.p. for the picrate was 161°C (147), 2) Acenaphthenequinone Twenty-five grams of Eastman-Kodak acenaphthenequinone which melted at 265-270°C with some previous softening, was extracted with diethyl ether in a Soxhlet extractor for a day in order to remove im-purities. The solid residue from the extraction (98.4%) was re-fluxed with charcoal in 3 liters of glacial acetic acid. The hot solution was filtered through a previously warmed Buchner funnel and the product crystallized as long yellow needles on cooling the filtrate to room temperature (yield: 71,2%; m.p, 275-276°C). After a second recrystallization from 1,5 liters of glacial acetic acid the overall yield was 59,3%; m,p» 273-274°C, The reported m.p. was 261° (132), -57-3 + log p 2-4- IOO IOOO p(mm.) 10 107 T l°k) 300 200 50 FIGURE 6 ACENAPHTHENE COX DIAGRAM. 109-113' 130-150° 4 - 6 mm. FIGURE 7 ,150-200° oi' both. J ACENAPHTHENE VACUUM DISTILLATION APPARATUS - 58 -Calculated for C^HgOg. C, 79.1%; H, 3.20%. Found: C, 78.8, 79.0%; H, 3.44, 3.38%. This material was used for the synthesis of acenaphthene-1,2-diols. The ether extract of the crude acenaphthenequinone (1.6%) contained some impurities as well as some acenaphthenequinone and was worked up in the following way: Concentration of the ether extract caused precipitation of 307 mg (1.18%) of a yellow solid which was recrystallized from 125 ml of a mixture of ether, methanol and benzene (2:2:1); yield 224 mg, m8p. 257.5-264.0°C. The filtrate after complete evaporation yielded a yellow crystalline solid residue (109 mg) which, after recrystalliza-tion from 70 ml of a 5:2 mixture of ether and methanol melted at 267.5-270.0°C. Further recrystallization from ether methanol gave yellow crystals (3 mg) melting at 247-253°C. A comparison of the infrared spectra of this sample with those of the original crude quinone and the twice recrystallized pure product clearly indicated that the ether extraction had removed some of the impurities from the crude quinone. 3) Oxidation of Acenaphthene This preparation was carried out in six experiments from a total of 418 g of acenaphthene, according to the procedure given in Organic Syntheses (131). The acenaphthenequinone was removed from the crude, solid oxidation product by repeated extraction with a hot 40% solution of sodium bisulfite instead of the single "bisulfite-extraction" recommended in the original procedure. From the bisulfite addition compound the acenaphthenequinone was liberated by treatment - 59 -with concentrated sulfuric acid. After digestion for 15 minutes the precipitated quinone was filtered off, washed with dilute ammonia solution, and finally with water and dried at 105°C. The yields of crude material obtained in successive "bisulfite extrac-tions" aresshown in Table XIV. The crude products were exhaustively extracted with ether in a Soxhlet apparatus (2 days) and then recrystallised from 80 parts of glacial acetic acid. The yields and melting points of the pre-parations are shown in Table XV. The overall yields were: fi r s t crop 164.16 g (33.2%); second crop 25.01 g (5.1%). The infrared spectra of those preparations indicated that they were impure acenaphthenequinone. 4) Cis- and Trans- Acenaphthene-1,2-diols Three different methods were tried for the reduction of the ac enaphthenequinone. (a) Reduction with Hydrogen Three hydrogenations were carried out according to the procedure of Jack and Rule (113) with five to six miligram samples of pure acenaphthenequinone and 60 mg. of platinum oxide catalyst (Brickman & Company, Montreal) in ethanol solution under 45-60 p.s.i.g. pressure. In each case the products turned yellow (m.p. 249-250°C) and the colourless diols could not be isolated by recrystallization. (b) Reduction with Lithium Aluminium Hydride About 15 g of finely pulverized lithium aluminium hydride (Metal Hydride Inc; Purity 95%) was slurried in 750 ml of dry diethyl ether which was rapidly stirred by a magnetic stirrer and refluxed in - 60 -Table XIV Yield and Melting Point of Crude Oxidation Product of Acenaphthene Acenaph- Yield from First Bi- Total Yield from Three Bisulfite Oxidn. thene sulfite Extraction Extractions (grams) grams % m.p. grams % min. & max. 1 30.1 10.0 28.1 l.-r- 10.0 28.1 2 60.9 27.2 37.8 227- 44.4 61.7 224, 259°C 231 °C 3 60.0 24.5 34.6 250- 36.6 51.7 250, 260°C 253°C 4 90.0 48.9 46.0 253- 92.4 86.8 222, 257°C 257 °C 5 90.0 46.9 44.1 --- 75.1 70.6 6 86.8 45.3 44.2 *m a* *• 57.4 55.9 _ _ _ Total: 417.8 202.8 41.6 340.6 69.0 - 61 -Table XV Yield and Melting Point of Purified Oxidation Product of Acenaphthene Crude Yield from Recrystallization* No. Sample First Crop Second Crop (gram) grams % m.p. grams % 1 10.00 7.06 70.5 263.5-265.5°C 2 30.30 21.62 71.4 262-263°C 4.30 14.2 3 29.99 21.14 70.5 262PC 5.34 17.8 4 29.99 21.26 70.9 264-266° 4.24 14.2 5 30.00 21.91 73.0 260-261.5° 4.46 14.9 6 30.00 21.68 72.3 263-264° 3.45 11.5 7 30.00 21.78 72.6 259-261° 3.22 10.7 8 36.66 27.71 75.6 260-261° * based on the weight of crude sample. - 62 -an atmosphere of purified nitrogen. After refluxing for an hour a suspension of 25 grams of acenaphthenequinone (m,p. 273-274°C) in one l i t e r of dry ether was added in small portions to the slurry through the central neck of the flask. The addition required about one hour and the s t i r r i n g and refluxing were continued for an additional 3 hours. In order to decompose the excess of lithium aluminium hydride at the end of the reaction, 1350 ml of 10% ( v/ v) solution of dry ethylacetate in ether was added slowly to the reaction mixture from a dropping funnel and f i n a l l y 450 ml of 15% sodium hy-droxide solution was added to destroy the complex. The aqueous layer was extracted six times with 500 ml portion of ether and the combined ethereal extracts after evapora-tion yielded 17 grams (66,9%) of a pale yellow, solid mixture of c i s - and trans- acenaphthene-1,2-diol, The use of a continuous liquid-liquid extractor increased the yield to 897. of the theoretical value. The separation of the two isomers was based on their different so l u b i l i t i e s in methanol. After recrystallization the pure isomers were obtained: Cis-acenaphthene-1.2-diol; yield:2,7 grams (10,4%); m.p, 218.0-219.5°C; reported m.p. 212°C (U3). Calculated for C12 H10°2 : C> 7 7» 4 7'» H> 5«41£> Found: C, 77.2, 77.0%; H, 5.39, 5.49%. Trans-acenaphthene-1,3-diol; yield 7.8 g (30.2%); m.p, 160.0-163.0°C; reported m.p. 159.5°C (113). Found: C, 77.3, 77.1%; H, 5.39, 5.29%. - 63 -(c) Enzymatic Reduction A reduction method used for keto steroids according to Mamoli (134) was applied for the reduction of acenaphthenequinone. In a 15 liter Pyrex bottle 300 grams of sucrose was dissolved in 4.5^ap water and 90 ml of M/15 potassiumdihydrogen^ phosphate, 90 ml of M/15 disodium hydrogeng phosphate, 14,6 g of "Fleischmann's active dry" yeast (Standard Brands Ltd., Montreal) and 3 grams of ace-naphthenequinone (m.p. 252-255°) were added. For stirring and to avoid contamination of the yeast culture a slow stream of purified nitrogen gas was passed into the mixture. After incubation for 2.5 days most of the quinone had dissolved and a further 300 g of sucrose was added and the fermentation was continued for a further 7 days. The filtrate from the reaction mixture was adjusted to pH 10 with concentrated sodium hydroxide solution and extracted six times with 500 ml of diethyl ether. The combined extracts were filtered and evaporated to small volume and the ether solution was kept in the re-frigerator at 44°C overnight:. The crystalline product which formed was collected and recrystallized from methanol to yield 110 mg of cis-acenaphthene-1.2-diol (m.p. 211-213°C). Evaporation of the ethereal mother liquor yielded a yellow solid which was recrystallized from aqueous methanol to give 507 mg (16.5%) of trans-acenaphthene-1,2-diol (m.p. 159-160°C). - 64 -5) Diacetates and Dibenzoates of the Acenaphthene-1.2-diols The following general procedure was applied: One mil|lmole (186 mg) of diol was dissolved in 10 ml of dry benzene and 2,5 mM(0.50 ml benzoylchloride; 0.18 ml acetyl-chloride) of acylchloride and 5.0 mM (0.4 ml) of dry pyridine (from calcium hydride) were added to the solution. After standing over-night at room temperature the mixture was refluxed for 2 hours on a steam bath. The mixture was diluted with 10 ml of water and ex-tracted exhaustively with ether. The solid residues obtained on evaporation of the washed and dried ether solutions were recrystal-lized from methanol. The liquid trans-acenaphthene-1.2-dioldiacetate was d i s t i l l e d on microscale at 0.02 mm pressure at about 108°C (bath temperature). The infrared and ultraviolet spectra of these deriva-tives were recorded. The cis-diacetate melted at 134.5-136.5°C. The reported m.p. was 130°C (148). The cis-dibenzoate melted at 148.0-149.5°C. The trans-dibenzoate melted at 132.0-134.0°C. The last two compounds have not previously been reported. 6) Acetonation of the Acenaphthene-1.2-diols Isopropylidene Cis-Acenaphthene-1.2-diol Approximately 10 mllimole (i„85g) of cis-acenaphthene-1.2-diol and 60 mg of p-toluene sulphonic acid monohydrate were suspended in a mixure of 40 ml of dry acetone ( d i s t i l l e d from calcinated potas-sium carbonate (139)) and 40 ml of dry petroleum ether (b.p. 30-60°) (from sodium wire). The mixture was refluxed in an apparatus described by Newman and Renoll (142) and modified by Christian, Gogek, and Purves (141), After a 4 hour refluxing period the c i s - d i o l had dissolved and 65 -the refluxing was continued overnight. The solution was neutralized by addition of a slight excess of anhydrous sodium acetate (60 mg) and was then treated with charcoal, filtered and evaporated to dryness. The colourless oily residue crystallized on standing in a dessicator. After recrystallization from petroleum ether (b.p. 30-40°C) there was obtained 800 mg of a colourless crystalline compound with a faint odour resembling camphene (m.p. 76-78°C)<> Calculated for C 1 5H 1 40 2: C, 78.97.; H, 6.187.. Found: C, 78.9, 79.07.; H, 6.31, 6.36%. Acetonation of trans-Acenaphthene"1.2-diol A mixture of 187.0 mg of trans-diol and 3 mg of p-toluene sulfonic acid monohydrate was refluxed in 8 ml of a 1:1 mixture of acetone and petroleum ether for 77 hours as described for the cis-isomer. The reaction mixture separated into a dark resin-like mass and a coloured solution. The solution was decanted and the resin was washed with boiling petroleum ether. The combined solution and washings were neutralized with sodium acetate, treated with charcoal, and eva-porated to give 56 mg of crystalline material. After two recrystal-lizations from ether the colourless product (25 mg) melted at 36-37°C„ The resin (133.2 mg) dissolved in benzene and after charcoal treatment and evaporation 85 mg of crude trans-acenaphthene-1.2-diol was recovered. The product melted at 150-153°C. after two recrystallizations of ether. In a second similar experiment 3.723 g of trans-diol and 60 mg of acid catalyst were refluxed in acetone-petroleum ether. Petroleum ether was added to the solution from time to time to test for unreacted diol which precipitated when the concentration of hydrocarbon was in-creased. The excess petroleum ether was then permitted to escape from - 66 -the condenser until a homogenous solution was again obtained after 1250 hours. The brown solution was evaporated under reduced pressure and the dark colored residue was extracted with petroleum ether. The yellow extract was worked up as in the first experiment to yield 10,2 mg of pure cis-acenaphthene-1,2-diol which melted sharply at 212°C. The infrared spectrum of this product was identical to that of authentic cis-diol. The residue from the petroleum ether extraction was dissolved in benzene and one third of the benzene solution was worked up as before to give 10 mg of crystalline product which melted at 343-344°C after recrystallization from acetone. The remaining two thirds of the ben-zene solution was fractionated on an acid washed alumina column and developed a series of organic solvents of increasing polarity. The several column fractions yielded dark amorphous residues on evaporation. From the residue of the benzene fraction a few crystals of cis-acenaphthene-1,2-diol separated by extraction with ether-petroleum ether (m.p. 212.5 -214.5°C). The remaining products were not identified. 7) Action of Phosgene on Acenaphthene-1.2-diols Phosgene from a cylinder (The Matheson Co., Inc., East Rutherford, N.Y.) was led through a purification train (trap, concen-trated sulfuric acid, trap) into a reaction flask which had previously been swept free of air by a stream of pure nitrogen gas. The flask was fitted with a reflux condenser and the excess phosgene was led from the top of the condenser to a trap which contained sodium hydroxide solution. - 67 -One hundred miligrams (0.54 mm) of cis-acenaphthene-1,2-diol (mep. 211o5-212.0°C) was dissolved in 20 ml of dry pyridine and dry phosgene gas was passed through the solution for 15 minutes. The red dish reaction mixture which had a rubber like foam on the top was left to stand for 1.5 days in a well-stoppered flask. In order to remove the excess of phosgene air was bubbled through the mixture for an hour, then 20 ml of absolute methanol was added and the solu-tion was evaporated in vacuo. The methanol addition and evaporation was repeated. From the oily product the carbonate ester was extracted with four 50 ml portions of boiling benzene. After removing the benzene in vacuo the crude product was recrystallized from benzene; yield 51.8 mg (44.47.); m.p. 231.0°C. Calculated for C13Hg03: C, 73.67.; H, 3.797.. Found: C, 73,6, 73.47.; H, 4.05, 3.977.. Cis-acenaphthene-1.2-diol carbonate (12.5 mg) in one ml of acetone was hydrolyzed with 1.5 ml of 0.2 N methanolic barium hydroxide solution according to Haworth and Poster (149). The recovered cis-diol after recrystallization melted at 205-207°C, Trans-acenaphthene-1.2-diol was treated with phosgene in the same way as above using the same quantities. The product obtained (58.5 mg) was a brown o i l , viscous o i l . The product was examined by paper chromatography and the Rp values were compared with those of the other acenaphthene derivatives (Figure 8). 8) Acenaphthene-1.2-diol Dinitrates  Nitration of cis-Acenaphthene-1.2-diol About twenty milimoles (3.719) of cis-acenaphthene -I: ,2-dip1 (m.p, 218,0-219.5°C) was nitrated in a mixture of 66 (3.8 ml) of -68-F1GURE 8 PAPER CHROMATOGRAM OF PRODUCTS FROM THE ACTION OF PHOSGENE ON ACENAPHTHENE-1,2- DIOLS. (1) Cis-Acenophthene-u2-diol W white fluorescence (2) Cis. Acenaphtene-1,2-diol carbonate B blue fluorescence (3) Trons- Acenophthen-1,2- diol Br brown absorption (4) Product from PhosqeneSTrons-diol reaction - 69 -glacial acetic acid, 80 vM (3.4 ml) of nitric acid (100%) and 400 vM (38,0 ml) of acetic anhydride. The nitrating mixture was cooled to -14°C (ice-salt bath) and the solid diol was added to the mixture with constant stirring over a period of 17 minutes while the temperature was maintained at -10 to -14°C. The stirring was continued and the temperature was allowed to increase slowly to +8°C. At 100 minutes reaction time the mixture was transferred to a continuous liquid extractor containing about 250 g of crushed ice. After exhaustive extraction the ether extract was washed several times with dilute sodium hydroxyde solution until no more colour was removed by the alkali. The ether solution was then washed with water and dried over anhydrous magnesium sulphate. Distillation of the ether yielded a yellow-brown, viscous o i l , which was dried at 0,005 mm for 3 hours at room temperature and a further 3 hours at 60°C in order to remove the last traces of acetic anhydride. The semi-solid residue (5,198 g, 94.2%) was extracted with 60-70 ml portions of boiling anhydrous petroleum ether (30-60°C). The combined petroleum ether extracts yielded 3.803 g (68,9%) of a yellow crystalline solid (b) which was washed with 40 ml of cold (-5°C) absolute methanol (d). After drying the yield was 2,672 g (48.4%) of almost colourless crystals. The residue (c) from the petroleum ether extraction weighed 1,275 g(23.1%). The main product (2.672 g) was purified by chromatography on a 3.0 x 40.0 cm column of acid-washed alumina developed with ether-ethylacetate (9:1). After the first few ml of dark yellow effluent came the main band of nitrate in a 200 ml volume. The nitrate ester -70-• 1.00 0 . 8 0 0 . 6 0 -0.40 1 020 SOLVENT O o OOQO-- O 0 1 1 . i c ;—@—#— d e f g 0 . 9 0 -0 . 7 0 - -0 . 5 0 0 . 3 0 O . IOT F I G U R E 9 PAPER C H R O M A T O G R A M O F CIS-ACENAPHTHENE-1^-DIOL N I T R A T I O N P R O D U C T S . All spots were brown under U.V light except spots of starting line correspondingly trons-diol(o) which were fluorescent. i After standing 24hrs. the shaded spots turned from colourless to a permanent ocher yellow colour. The other remained colourless. was detected in the effluent by the U.V. absorption of spot on f i l t e r paper. Evaporation of the solvent mixture yielded 2.246 g (40.7%) of colorless crystals. After recrystallization from 35 ml of absolute methanol two crops were separated: (e) 1.026 g (18.6%), m.p. 126.0-129.0°C and (f) 0.355 g (6.4%), m.p. 90 - 109°C. Crop (e) was recrystallized from 20 ml of absolute methanol to give (g), 711.0 mg (12.9%), m.p. 128-130.5°C, Calculated for C12 H8°6 N2 : N> 1 0 « 1 5 % » Found: 9.93 + 0,07% (UltramicroKjeldahl). Nitration of Trans-Acenaphthene-1.2-diol About fifteen milimoles (2,720 g) trans-acenaphthene diol (m.p. 160 - 163°C) was nitrated as before with a mixture of 49,5 mM (2.85 ml) of glacial acetic acid, 60 mM (2.55 ml) of nitric acid (100%) and 300 mM (28.5 ml) acetic anhydride. The addition time was 18 minutes while the temperature was kept between -15 to -5°C. The total rSeaction time was 35 minutes when the temperature rose up +12°C. The reaction mixture was worked up as in the case of the cis-diol dinitrate. Crude yield was 3.809 g (92.0%). After extraction eleven times with 60-70 ml portions of boiling anhydrous petroleum ether (30-60°C) 3.370 g (81.5%) extract and 0.241 g (5,8%) residue were separated. fc<jiwa. t o ) Purification on a 5.0 x 20.0 cm acid washed alumina (E. Merck) column produced 1500 ml effluent (ether- ethylacetate 9:1) of the di-nitrate which after evaporation was recrystallized from 20 ml absolute methanol. Two crops were separated: 1.208 g (29.2%), melted at 96.5-98.0°C and 1.004 g (24.3%) with a m.p. 95.0-96.0oC. The -72-Yield No. of Extractions FIGURE 10 EXTRACTION OF DINITRATES WITH PETROLEUM ETHER (b.p.30-60°C ) - 73 chromatographic and recrystallization procedure were repeated two more times, the obtained final products were: 685 mg (16*5%), melted at 98.5-99.0°C and 330 mg (7.97%) melted at 98.0-95.5°C. Calculated for C12Hg06N2: N, 10.15%. Found: 10.17 + 0.23% (Ultramicro Kjeldahl). 9) Reduction of cis-and-trans-Acenaphthene-1.2-diol Dinitrates (a) Reduction with Sodium Borohydride Trans-acenaphthene-1.2-dioldinitrate in 5 ml absolute methanol was treated with 145 mg of sodium borohydride (3007. excess). After 2 hours reaction time (40°C) the mixture was acidified with 1 ml of acetic acid to pH 6 add evaporated to dryness. The residue was suspended in 30 ml of absolute methanol and the methanol was evaporated in vacuo.to remove the boric acid this procedure was repeated. After recrystallization from methanol the crystalline compound obtained melted in the range of 95-125°C. Paper chromatography and diphenyl-amine test indicated the presence of unreacted nitrate (Figure 11). (b) Reduction with Lithium Aluminium Hydride Three parallel reactions were carried out and the products obtained were compared by paper chromatography. About 82 mg of lithium aluminium hydride (957.) was suspended in 10 ml of dry ether and the mixture was stirred at room temperature under a nitrogen atmosphere. To the slurry 94 mg of trans-acenaphthene-1,2-diol dinitrate was added and the mixture was stirred for 1.5 hours and then transferred to a continuous liquid-liquid extractor. Five ml of 20% sodium hydroxide solution was added to the ethereal solution and the extraction was continued for 24 hours. Evaporation of theether - 74 -yielded 64.2 mg of residue which was recrystallized from methanol water. The colourless crystalline product (17.0 mg) melted at 110-145° and was examined on a paper chromatogram (Figure 11). (c) Reduction with Hydrogen  Preparation of Catalyst; Palladium charcoal catalyst was prepared according to Hartung (150) from '»Darco-G-60" (Atlas Powder Co., 60 East 42nd St., New York) reagent grade charcoal. The charcoal was previously agitated with 6N hydrochloric acid on a steam bath for a few hours and then washed with deionized water until the pH remained constant (pH5) and the effluent was free of chloride ion. About 1.20 g of purified Carco-G-60 charcoal and 110 mg of palladium chloride (Baker platinum of Canada Ltd., Toronto) were sus-pended in 100 ml of distilled water and shaken under 60 p.s.i.g. hydrogen pressure for 20 hours. The slurry (pH2) was filtered and washed with distilled water (250-300 ml) and with acetone (70-80 ml) and dried in vacuo over sulfuric acid., Hydrogenation of cis- Acenaphthene-1,2-diol Dinitrate: About 100 mg cis-acenaphthene-1.2-diol dinitrate and 100 mg of palladium charcoal catalyst were suspended in 50 ml of absolute methanol and shaken at room temperature under 60 p.s.i.g. hydrogen pressure for 200 rainutes«, The diphenylamin spot test (57) was posi-tive for nitrate (151) but paper chromatography showed the presence of cis-acenaphthene-1,2-diol in the mixture (Figure 12). The methanolic solution was filtered free of catalyst and the filtrate was evaporated -75-.00 0.80 0.60 040 SOLVENT A "Br Br Br 0.20 0B 0B 0B B B 6 i\N W B U B ^VIB ~ B TAD I 2 3 4 TA F IGURE SOLVENT 3 Br ^jBr Br .B r " i i n B B =f)B B B W B O o d 0 6 B ^ B B B O O O o o ° O-8—o§-o-B TAD I 2 3 TA 0.90 0.70 0.50 0.30 0.10 PAPER CHROMATOGRAM OF PRODUCTS FROM REDUCTION OF TRAN S - AC EN APHTHAE NE -1,2- DINITRATE (TAD) WITH METAL (l),(2),(3), L i A i r i 4 reduction (4) NaBH 4 reduction HYDRIDES bl ue l l l l blue Y IHI yellowJ by Diphenyl amine reagent B blue] W whit< Br brown absorption , V fluoresc enc e - 76 -in vacuo. The solid mass obtained was recrystallized from methanol to give 17 mg (25,3%) pinkish white long needles melting at 215-216°. The mixed m.p. with standard cis-acenaphthene-1.2-diol was 210.0-214.5°C. The infrared spectra (KBr) of the recovered and standard diols were identical. Hydrogenation of trans-Acenaphthene-1.2-diol Dinitrates The experiment was carried out precisely &n the same way with the same quantities as above. The recovered trans-acenaphthene-1,2-diol (26 mg; 38.5%) melted at 161.0-162.5°C. The mixed melting point with authentic sample was 159-161°C. The infrared spectra of the recovered and standard diol were identical. - 7 7T F 1.00 SOLVENT B W W . Q . Br 0.80 pa 'B B 0.90 Br BW 0.60 0.40 0.20 SI Br >Br FIGURE 12 A. cis-o. t ionj B. o s -trans b C. c. | Acenaphthene-1,2- diol | Hydrog e n a ti o n react.mix. c is - i — V Acenaphthen-1,2-diol Dinitrates trajis-J 0.70 0.50 0.30 0.10 PAPERCHROMATO GRAM OF HYDROGENATI ON PRODUCTS FROM DINITRATES W white B blue uoresc ence Y ye How Br brown absorption 111 blue 5H yellow | c'olour with Diphenylamine reagent. - 78 -B> ANALYSIS 1) Melting Point Determinations The corrected melting points were observed (+ 0,,5oC) with a hot-stage, a polarizing microscope (Nr. 48114; Ernst Leitz, Wetzlar, Germany). 2) Micro C-H Determinations Analysis for carbon and hydrogen were carried but by Dr. Alfred Bernhardt of Max Panck Institute, Kaiser WiUfcalm Platz 1, Mulheim (Ruhr), Germany. 3) Ultra micro Nitrogen Determination The well known micro-Kjeldahl procedure for nitrate nitrogen (44) (45) was modified according to aerecent publication of Tourtellotte, Parker, Alving, and De Jong (152) with a combination of the Nessler (153) colorimetric ammonia determination (154), so that the determination could be made on samples containing 20 to 160 micrograms of nitrogen. Reagents (1) Freshly distilled water (not older than 48 hrs) from an electrically heated Manesty (OB-008) water s t i l l . (2) Salicylic Acid Solution: Reagent grade salicylic acid (3.50 g) was dissolved in 100 ml of cold sulfuric acid and stored in a ground glass stoppered bottle 0 The solution was kept in a refrigerator and was satisfactorily good for several months. (3) Catalyst Solution: About 24.0 g of reagent grade potassium sulfate, 100 mg of commercial mercurochrome and 100 ml of reagent grade - 79 -concentrated sulfuric acid were shaken at room temperature for 12 hours. After a l l the materials went into solution 0*02 ml of selenium oxy-chloride (B.D,H0) was added to the mixture,, (4) Analytical reagent anhydrous sodium thiosulfate QMllinckrodt Chemical Works, Montreal). (5) Sodium Hydroxide Solution: About 4®£ solution was prepared by dissolving 100 g of reagent grade pellets in 150 ml of distilled water, (6) Hydrochloric Acid Solution: Approximately 0,1 N hydrochloric acid solution was prepared from concentrated reagent grade hydrochloric acid, (7) Nessler's Reagent: One hundred grams of mercuric iodide (Bakers Analyzed, Insolubles, potassium iodide solution 0,008%) and 70 g of potassium iodide were dissolved in 400 ml of water in one liter volumetric flask. After complete solution 100 g of sodium hydroxide in 500 ml water was added and after cooling the solution was made up with water. The opalescent solution next day was centrifuged and the supernatant liquid was stored in a brown, glass-stoppered bottle, (8) Standard "Nitrogen" Solutions: Both ammonium sulfate and potassium nitrate were used as nitrogen standard. Both compounds were purified by the dissolving reagent grade salt in distilled water, and after treatment with charcoal, the materials were precipitated by adding methyl alcohol. The samples were dried at 150°C before use and stock solutions were prepared so that the concentration of nitrogen was 1,00 mg per ml, Foom these stock solutions standard solutione (100 /Ag N/ml) were prepared by tenfold dilution. - 80 -Apparatus The Kjeldahl flasks and distillation apparatus as described by Tourtellotte, Parker, Alving and De Jong (152) were slightly modi-fied (Figure 13). Procedure If the material was in solution an aliquot was evaporated in the digestion flask under reduced pressure on a rotating evapora-tor. Solid samples were weighed directly on a "Cahn" electrobalance (+ 0,001 mg). Salicylic acid solution (0.20 ml) was added to the digestion flask which was rotated frequently to bring the solution into contact with a l l of the sample and was then allowed to stand for 30 minutes or more at room temperature. Approximately 10 mg of solid sodium thio-sulfate was added to flasks which were then heated gently for 2 to 5 minutes while most of the sulfuric acid evaporated. Finally 0,10 ml of catalyst solution was added to the black residues and the digestion was continued with gentle refluxing for two hours. At the end of the digestion and after cooling 1,0 ml of 40% sodium hydroxide was added and the ammonia was distilled into a 50 ml volumetric flask containing 5 ml of 0.1N hydrochloric acid solution. After about 20 ml of distillate had been collected, the distillation was complete. The distillate was made up to about 45 ml with distilled water, 2,00 ml of Nessler's reagent was added, and the solutions were made up to the mark. After 10 minutes from the addition of the f i r s t of the Nessler solution the optical densities of the yellow - 82 -solutions were read at 405 m on a Bausch and Lomb "Spectromic 20" colorimeter-spectrophotometer. At least two blanks were required for each series of determinations. Standard deviations were determined from the observed values and the calibration curve which passed through the 0,260 6. value at the 60,0 /UgN/50 ml concentration (Figure 14), The standard devia-tions for different ranges are shown in Table XVI, Isoidide dinitrate (m.p, 6fr«9S0c [°<\+ 72,9°) (13) was used as covaient nitrate standard. The results of the analysis shown in Table XVII are compared with previously obtained values. - 8 3 --0.70 -0.60 - 0.50 •0.40 .0.30 -0 .20 - 0.10 20 — u - 40 L _ 60 — u - 80 — 4 — 100 I 120 i 140 i 160 i • FIGURE 14 JUQU/50m\ CALIBRATION CURVE FOR AMMONIA - NESSLE R'S RE AGENT AT 405 m/U. A standord (NH4)2S04 solution O standard KNO^ solution - 84 -Table XVI Standard Deviations of Ultramicro Nitrogen Determinations Concentration u^gN/50 ml Standard Deviation 0-60 + 4.22% 60-160 + 1.62% 0-160 + 2.71% Table XVII Nitrogen Analyses on Isoidide Dinitrate THEORETICAL STANDARD DUMAS ULTRAMICRO N% MICRO-KJELDAHL COMBUSTION KJELDAHL (a) (b) (c) 10l8% 11.16% 11.89% 11.85% 11.83% 11.3% 11.39% 11.80% AVERAGE 11.1% 11.28% 11.84 + 0.05% (a) Analysis by Dr. M. Jackson in this Laboratory (b) Analysis by Dr. A. Bernhardt (c) This work - 85 -C) SPECTRA 1) Ultraviolet Spectra A l l UoV, spectroscopic measurements were made on a Cary recording spectrophotometer (Model 14) in 95% ethanol solution, using the same solvent as blank in the reference beam. The base line was determined with two blanks and the spectra were corrected with the corresponding values. The concentration of a l l solutions was bet-ween 0,08 and 0,12 mM/1, From the obtained €max values the mole-cular extinction coefficients were calculated. Table XVIII includes the constants for Acenaphthylene also measured in cyclohexane solu-tion (89), The values for Acenaphthene;in ethanol) were reported by Jones (155), 2) Infrared Spectra A l l the infrared spectra were taken in the solid state with potassium bromide on the Perkin-Elmer Model 21 Infrared spectro-photometer. The windows contained approximately 400 mg of dry potassium bromidee The weight of the substance was usually between 0,5 - 1,0 mg. The specification for the spectra were as follows: "prism: NaCl, resolution: 927, response:1, gain 6, speed: 2-8, suppression: 2, The spectra obtained were qualitative. The accuracy of the frequency readings were at 0 s 600-2000 cm""1: ^> *» + 1 cm"1 at 0 = 2000-4000cm"1: A\> = + 4 cm'1. The reproduced spectra were taken on the Perkin-Elmer "Infracord" spectrophotometer from the same windows but the recorded frequencies were obtained from the larger instrument mentioned above. - 86 -Table XVIII Obtained Acynaphthylene Reported 3240 6 i 13860 Acenaphthene 2892 3026 6496 5813 2890 6457 Acenaph thenequ inone 3133 5962 cis-Acenaphthene-1,2-dio1 2853 5995 trans- it 2863 6091 - - -cis-- II dinitrate 2853 7550 trans- •i dinitrate 2865 7980 cis- it diacetate 2847 7585 - — trans- II diacetate 2851 7860 cis- II dibenzoate 2853 8673 trans - II dibenzoate 2853 10786 _ _ _ - 87 -D) PAPER CHROMATOGRAPHY For a l l the experiments Whatman No, 1 paper was used. Three solvent systems were found to be suitable for the acenaphthene derivatives: (A) pet, ether-methanol-water-(10:4:1) (13), (B) water-n-buthanol-ethanol-conc. ammonia-(49:40:10:l) (9), (C) benzene-glacial acetic acid-water-(8:2:1) (156), and were used extensively in this research. Other solvent systems were tried such as: (D) pet, ether-N,N-dimethylformamide-(2:l) (157), (E) water-n-buthanol-conc, ammonia-ethanol-(8,33:4:1,67:1) (158), (F) pet, ether-acetone«water-(1.44:1.44:l) (159), (G) pet, ether-acetone-water-(l:l:l), (H) pet, ether-acetone-methanol-water-(10:2:2:l), (I) pet, ether-n-buthanol-water-(10:4:l), (J) benzene-pet, ether-glacial acetic acid-water (6:2:2:1), but the results obtained were not satisfactory. As was suggested by Jackson (13) the low priced petroleum ether (b.p, 67-68°C) was used instead of pure n-hexane. Al l the distances were measured and a l l the flow ratios were calculated to three significant figures. Instead of the con-ventional Rp values the modified Rp values were calculated according to Evans and Reith (160) which were defined by the following equation: RF ne Dist. travelled by spot front  Dist, travelled by solvent front - 88 -Paper chromatograms were developed by the descending method in a glass tank with the top layer of the solvent mixtures. The bottom layers were placed in a flat dish in the bottom of the tanks for establishing vapour equilibrium. The location of the spots on the chromatogram was determined under a U,V, lamp (Mineralight, Model: V43, Los Angeles, Calif,), The RF values obtained are shown in Appendix 4, - 89 -E) THE REACTION OF PYRIDINE WITH THE ACENAPHTHENE-1,2-DIOL DINITRATES 1) Preliminary Experiments (a) One ml of 0,1 M cis- and trans-acenaphthene-lf 2-dlol dinitrate solutions in pyridine vere prepared in open tubes (6 x 190 mm). After standing for 50 minutes (t 0) at room temperature the solutions vere refluxed by heating the lower ends of the tubes in an o i l bath0 Aliquots of the reaction mixtures (0.1 ml) vere vithdravn at 0.5 ( t x ) , 1,5 ( t 2 ) , 4.0 ( t 3 ) , 10,0 (t 4) and 25,0 (t^) hours and transferred to 1 ml of 3N sulfuric acid solution, A yellov precipitate appeared immediately in each case. The mixtures vere extracted three times vith 1 ml of ether. The ether extracts vere evaporated to dryness and the residues vere taken up in acetone and the acetone solutions vere made up to 1,00 ml. These solutions vere used for qualitative paper chromatographic analysis (Figures 15 and 16), (b) Pyridine solutions of the acenaphthenediol dinitrates on storage at -20°C for 25 hrs, shoved a faint yellov colour and gave a positive test for nitrous acid (145), (c) Ten micromoles of trans-dinitrate was dissolved in 0,1 ml of dry pyridine in a thin walled reaction tube (5 x 50 mm) and the tube was sealed immediately, placed in a small liquid-liquid extractor containing 2 ml of 2N sulfuric acid and the tube was crushed - 90 -under the sulfuric acid solution 0 This operation required less than 2 minutes from the fi r s t contact of the nitrate with pyridine. The acid suspension was extracted with ether for 5 hrs and the extract was transferred to a 1 ml volumetric flask and evaporated in a stream of purified nitrogen gas. An acetone solution of the residue was prepared as described in section (a) above. Paper chromatograms prepared from duplicate solutions (solvent C) showed two new reaction products at Ry = 0,89640,016 and Rp = 0,52440,002 which displayed a white fluorescence under the U.V, lamp, in addition to the spot for unreacted trans-acenaphthene-1.2-diol dinitrate (Rp a 0,960 + 0*009), Spectrophotometry estimation on the nitrate spot (see below) indicated that only 75% of the trans-dinitrate was recovered. The extensive decomposition of the nitrate was attributed to the increase in temperature which occurred during the sealing of the reaction tubes, 2) Rate Studies of the Reaction In these experiments the reactions were carried out in a micro, a l l glass, liquid-liquid extractor. Ten milimoles (2 , 9 6 mg) of dinitrate was weighed directly into the delivery tube of the extractor and 100 yul of dry pyridine was added from a calibrated capillary micropipette. The reaction vessel closed with a ground glass stopper and placed in a constant temperature bath (25,2 + 0,1°C), The reaction was stopped by addition R F Moo SOLVENT Br Br SOLVENT B \ B r _ B r w O O O O o o O o 0 o o o o S O L V E N T C 0 B r Q s r O O 8Br Br 'BOBQ , O ow a o o o o o "b o o o vo o Y 0 O o C A 0 t, ti t, t„ t, d c*o t„ t, t3 t, t3 3. CAD t„ t, tL t5 t„ t5 Q FIGURE 15 PAPER CHROMATOGRAMS OF ETHER SOLUBLE PRODUCTS OF THE REACTION OF C I S - AC ENA PHTHEN E-1.2-DIOL DINITRATE WITH PYRIDINE. CAD: cis dinitrote Q.- quinone 4 F U.00 S O L V E N T C Br U • S O L V E N T B r\B,oBr o o n o o 0 ,° o o 0Y 0' -o-o-o—•—o—o S O L V E N T C o o B r B o B O OY O O O Br o o o Y Br O 0 Y -OO—o—•—o—o r A 0 ti t, U tr a rAp t± t, tt t3 ti, tr a r*o ta t, *-2 t 3 t„ ta- 3 FIGURE 16. T R A N S - D I N I T R A T E AS FOR F I G U R E 15 - 9 3 -of 2 ml of 2N sulfuric acid. Ether was added through the delivery tube u n t i l the boiler flask was h a l f - f i l l e d and the acidic mixture was exhaustively extracted in the usual mannere The reaction time was measured from the time when the nitrate completely dissolved in the pyridine to the time when the f i r s t precipitate appeared after the sulfuric acid additions The ethereal extract was worked up as before and the dry residue was dissolved in warm benzene and.after cooling was made up to 1,00 ml. Four 0,01 to 0,10 ml aliquots of the benzene solution were spotted on Whatman paper and the chromatograms were developed with solvent C, A typical chromatogram i s shown in Figure 17, The undecomposed dinitrate was determined by UV absorption spectrophotometry after location of the spots under the UV lampe The area of the outline spot was determined by tracing i t onto twenty-pound bond paper e The copied spot was cut out from the bond paper and was weighed on an analytical balance. This weight was converted to area of spot by means of the factor 1,0000 g = 120,2 cm' which was determined by weighing a series of pieces of the paper of known area, A portion of the nitrate ester spot was cut out from the f i l t e r paper by following a rectangular template, located so that the center of the nitrate spot would intercept the beam of light in the spectrophotometero A strip of paper of the same size (12 x 50 mm) was cut from the parallel position on the chromatogram and was used as a blank in the spectrophotometer. - 94 -A few minutes before the determination the paper strips were painted with Nujol and a few seconds before the determination the excess Nujol was removed by wiping with a piece of Kleenex© The blank and the sample were placed in the 0,5 cm cell holder and the spectra were recorded from 3500 to 2000 A (speed 20, Cary spectrophotometer). From the spectra obtained which were very simi-lar to those taken in solution the value of € was determined as the difference of <= max - 6 3500, Since the area of the spot on the paper strip through which the light beam passed was 1,44 cm , g*, the logarithm of the intensity of the light absorbed by the total nitrate spot was obtained from g* =<g6 , where: <^> a spot area (cm ) 1,44 cm^  Calibration curves (Figure 18) relating e* to micromoles of nitrate ester were prepared from measurements on chromatograms loaded with known amounts of nitrate esters. Standard deviations of the individual readings from the calibration curve are shown in Table XIX. - 9 5-I.OC 0.80--0.6O-0.40-0*20-•0.90 •0.70 • 05 0 - 0.30 -0.10 cis trans FIGURE 17 PAPER -CHROMATOGRAM OF ETHER SOLUBLE PRODUCTS OF THE REACTION CJS-AND T R A N J - ACENAPHTHENE-I^-DIOL DINITRATE WITH PYRIDINE AT 25°C AFTER 30 MINUTES TABLE XI X STANDARD DEVI AT I ATI AT IONS FOR NITRATE ESTER DETERMINATIONS ON PAPER CHROMATOGRAMS Observed Maximum Standard Deviations Dev cis-Acenophthenedioi Dinitrate +8. 9 7 % *, - 9 . 8 6 % 17.87% trans-Acenaphthenediol Dinitrate +-3. 3 3 % ; - 10.00% 46.52% -96-97 -A P P E N D I C E S - 98 -APPENDIX 1 Calculation of Bond Angles of Acenaphthene The bond lengths (Angstroms) in Figure 20 for the acenaph-thene molecule were obtained from X-ray diffraction data for acenaphthene, naphthalene, and toluene (77) (123) (124) as described in the section on Results and Discussion a = 180°-VI From the law of cosines 2»352 = 1.422 + 1.352 + 2x1.42x1.35xcosa whence a = 63° 06' and VI = 180° - a = 116° 54' V s 90° 4- a, From the law of sines 2.35 . 1.35 whence a, = 30° 49' and V = 90° + a, « 120° 49' sin 116°54' sin a x I a 90° + a 2 and 116° 54* + 30° 49' + a2 - 180° 00' * whence Ct2 = 32° 17' and I = 90° + a2 • 122° 17' B = 180° - III and 2.352 « 1.422 4- 1.362 4- 2 x 1.42 x 1.36x cos B whence B = 65° 511 and IV = 90° + ^  = 121° 51* II . 90° + B 2 and 114° 09' 4- 31° 51' 4- B 2 = 180° 00' whence B 2 = 3 4 0 0 0 ' **d II = 90° 4- B = 124° 00' a m 360° - IV - V . 117° 20' and Vz « 58° 40* therefore sin 58° 40' 2 and a = 2.43 2 x 1.42 y = 1.522 - 0.392 = 1.46 c a 90° +t and cos if = 1.46 whence 1.52 tm 16° 09* and c « 90° 4- t . 106° 09* b . <5 + 6 , € = 90° - a / 2 = 90° - 58° 40* = 31° 20* and $ = 90° - i f « 90° - 16° 09* « 73° 51' whence b = 5 4 - 6 = 73° 51' 4- 31° 20' = 105° 11* -99 -FIGURE 19 G E OMETTRY OF ACENAPHTHENE - 100 -Appendix 2 Infrared Spectra of Acenaphthene Derivatives Summary Compound Spectrum No, Figure Table* Acenaphthene Acenaphthenequinone (purified Erk.) Acenaphthenequinone (synthetic) Impurity removed from crude E.K. acenaph-thenequinone cis-Acenaphthene-1,2-diol trans-Acenaphthene-1,2-diol cis-Acenaphthene-1.2-diol carbonate cis-Acenaphthene-1,2-diol acetone compound cis-Acenaphthene-1,2-diol diacetate cis-Acenaphthene-1, 2 -diol dibenzoate trans-Acenaphthene-1,2-diol diacetate trans-Ac enaphthene-1,2-diol dibenzoate cis-Acenaphthene-1,2-diol dinitrate trans-Acenaphthene-1.2-dinitrate 1 2 3 4 5 6 7 8 9 10 11 12 13 14 20,22,23,24, IV 25,28,29,30 20,21,22,23 XX 21 XX 21 XX 22,24,25,26, XXI 28 23,27,29 XXII 24 XXIII 25 XXIII 26 XXIV 26 XXIV 27 XXIV 27 XXIV 28,30 XXV 29,30 XXV Al l frequencies in cm. 101 -Table XX Characteristic Infrared Frequencies of Different Samples of Acenaphthenequinone Purified E.K. From Oxidation of Impurity from Acenaphthenequinone Acenaphthene E,K. Quinone 1770 ( s ) 1770 (s) 1718 (s) 1718 (s) 1718 ( s ) 1605 (s) 1605 (s) 1605 (s) 1590 (s) 1590 ( s ) 1590 (s) 1515 (w) 1515 (w) 1490 (m) 1490 (m) 1490 (m) 1443 (w) 1443 (w) 1443 (w) 1423 (w) 1423 (w) 1423 (w) 1309 ( s ) 1307 ( s ) 1278 (s) 1278 (s) 1278 (8) 1233 (s) 1233 (s) 1214 (m) 1214 (m) 1214 (m) 1170 (w) 1170 (w) 1150 (w) 1150 (w) 1150 (w) 1125 <s) 1125 (8) 1075 (w) 1075 (w) 1059 (w) 1059 (w) 1059 (w) 1015 (s) 1015 (s) 1015 (8) 894 (s) 894 (s) 894 (s) 830 (s) 830 (s) 830 (8) 778 (s) 778 (s) 778 (8) 726 (w) 7726 (w) - 102 -Table XXI Characteristic Infrared Frequencies of Pure and Impure Cis-Acenaphthene-1.2-diol Pure Impure 3360 (s) 3360 (s) 3210 (s) 3210 (s) 3090 (w) 3090 (w) 2940 (w) 2940 (w) 1625 (w) . M f f 1603 (w) 1610 (w) shift 1592 (w) 1502 (w) s h i f t - 1513 (m) 1454 (w) 1454 (w) 1441 (w) 1441 (w) 1432 (m) 1366 (w) 1336 (w) 1335 (m) shift 1322 (m) 1262 (m) 1262 (m) 1238 (w) 1226 (w) 1226 (w) 1216 (w) 1216 (w) 1206 (w> 1206 (w) 1179 (m) 1179 (m) 1159 (m) 1159 (m) 1124 (m) 1124 (m) 1104 (s) 1104 (s) 1064 (w) 1064 (w) 1038 (w) 1038 (w) 1016 (s) 1000 (s) 973 (w) 973 (w) 910 (w) 910 (w) 865 ( 8 ) 865 (s) 782 (s) 782 (s) 750 ( 3 ) 750 (s) 723 (m) - 103 -Table XXII Characteristic Infrared Frequencies of Pure and Impure Trans-Acenaphthene-1.2-diol Pure Impure 3260 (s) 3260 (s) 3060 (w) 3060 (w) 2900 (w) 2900 (w) 1626 (w) 1626 (w) 1614 (w) 1614 (w) 1498 (m) 1498 (m) 1341 (m) 1341 (m) 1320 (w) 1320 (w) 1300 (w) 1300 (w) 1264 (w) 1264 (w) 1240 (w) 1240 (w) 1210 (m) 1210 (m) 1205 (w) 1205 (w) 1177 (m) 1177 (m) 1152 (m) 1152 (m) 1115 (s> 1115 (s) 1093 (s) 1093 (s) 1040 (m) 1040 (m) 1031 (s) 1031 (s) 998 <s) 998 (s) 914 (w) 914 (w) 896 (w) 896 (w) 865 (w) 865 (w) . . . » 228 (w) 807 ( 8 ) 807_(s) 775 ( 8 ) 775 (s) 750 (w) 750 (w) 104 -Table XXIII Character i s t i c Infrared Frequencies of Acenaphthene-1,2-dlol C y c l i c Der ivat ive Carbonate Isopropylidene Aceta l 1823 (s) 2980 (w) 1795 (s) 2910 (w) 1774 (s) 1500 (w) 1742 (m) 1458 (w) 1500 (w) 1438 (w) 1366 (w) 1380 (s) 1355 (s) 1373 (s) 1316 (m) 1273 (m) 1273 (w) 1257 (s) 1180 (m) 1200 (s) 1168 (s) H78 (s) 1065 (s) l l 6 0 (*) 1017 (m) H 5 0 (s) 952 (m) 1110 (w) 875 (m) 1063 (s) 832 (m) 1017 (w) 785 (s) 1007 (s) 771 (s) 968 (m) 728 (m) 919 (m) 692 (w) 8 9 7 <*) 873 ( s ) . 861 (s) 836 ( s ) . 808 (s) 800 (s) 783 (s) 681 (w) 660 (w) - 105 -Table XXIV Characteristic Infrared Frequencies of Acenaphthene-1.2-diol Esters cis-Diacetate trans-Diacetate cis-Dibenzoate trans -Dibenzoate 3050 (w> 1440 (w) 1724 (s) 2915 (w) 1750 (s) 1377 (m) 1702 (s) 1715 (s) 1613 (w) 1345 (w) 1602 (m) 1708 ( 8 ) 1503 (*) 1283 (s) 1498 (w) 1600 (m) 1422 (*) 1220 (s) 1458 On) 1581 (w) 1375 (s) 1157 (w) 1345 (m) 1492 (w) 1335 (m) 1107 (w) 1317 (*) 1453 (m) 1230 (s) 1064 ( 8 ) 1290 (s) 1373 (w) 1175 (s) 1030 (s) 1273 (s) 1318 ( 8 ) 1150 (s) 997 (w) 1255 (s) 1273 (s) 1113 (m) 938 (m) 1180 (m) 1270 (s) 1065 (s) 890 (w) 1120 (s) 1248 (s) 1040 (s) 867 (w) 1100 (m) 1227 (m) 995 (nO 814 (m) 1073 (v) 1273 (*) 965 (w) 773 ( 8 ) 1054 (w) 1107 (s) 942 (s) 762 (s) 1025 (w) 1097 (s) 9909 (w) 718 (w) 1000 (w) 1070 (s) 900 (w) 645 (w) 898 (m) 1028 (s) 867 (w) 864 (w) 998 (m) 858 (v) 836 (w) 958 (m) 818 ( 8 ) 822 (m) 903 (w) 810 (m) 788 (s) 841 (m) 776 (s) 740 (m) 816 (s) 740 (m) 712 (s) 783 ( 8 ) 672 (w) 684 640 (w) (w) 769 726 718 708 668 (m) (s) ( 8 ) (s) (w) - 106 -Table XXV Characteristic Infrared Frequencies of Acenaphthene-1,2-diol Dinitrates cis-Dinitrate trans-Dinitrate 1650 (s) 1655 (s) 1627 (s) 1622 (s) 1503 (w) 1504 (w) 1425 (w) 1388 (m) 1332 (m) 1348 (w) 1927 (s) 1328 (w) 1280 (s) 1237 (s) 1273 (s) 1207 (w) 1179 (m) 1105 (w) 1106 (w) 1012 (m) 1054 (s) 970 (m) 1036 (m) 900 (m) 1023 (s) 865 (s) 995 (w) 847 ( 8 ) 910 (m) 812 (s) 870 (s) 777 (s) 848 (s) 758 (w) 830 (s) 751 (w) 807 (w) 713 (w) 790 fa) 643 (w) 778 (s) 762 (w) 755 (m) 731 (m) 670 (w) W A V E L E N G T H (MICRONS^) TiCURE. 2o. f/CrURe 23 7 8 9 10 WAVELENGTH (MICRONS) 17 12 13 14 IS* FIGURE 2± it. FIGURE 27 J J I J 1 1 1 I 1 1 — — I 3 4 5 6 7 8 9 10 11 12 13 14- . 15 WAVELENGTH (MICRONS) piQURE 29. F/GURS 30. - 118 -Appendix 3 Ultraviolet Spectra of Acenaphthene Derivatives Summary Spectrum No. Compound Figure No, 1 Acenaphthene 31 2 Acenaphthenequinone 31 3 cis-Acenaphthene-1.2-diol 32 4 trans-Acenaphthene-1.2-diol 32 5 cis-Acenaphthenediol diacetate 33 6 tr ans-Acenaphthenedlo1 diacetate 33 7 cis-Acenaphthenediol dibenzoate 34 8 trans-Acenaphthenedlo1 dibenzoate 34 9 cis-Acenaphthenedlo1 dinitrate 35 10 trans-Acenaphthenedio1 dinitrate 35 - 100-le 0.8 - H I -'S a* OH 0.2 2 500 3 5 o o K * ) - 124 -Appendix 4 Paper Chromatography of Acenaphthene Derivatives Samples were spotted from acetone or benzene solutions. The modified Rp values obtained are shown in Table XXVI. The stan-dard deviations from the average values were calculated by the con-ventional formula: where £ is the standard deviation, ^ is the individual deviation from the average Rp value and n is the number of experiments. The amounts of the substances which were spotted in quantitative paper chromatography (solvent C) were varied from 0.08 to 0.50 M per spot, however no significant relationship was observed between Rp values and these quantities. - 125 -Table XXVI Modified Rp Values for Acenaphthene Derivatives Solvent A Solvent B Solvent C n RF n Rp n Rp Acenaphthenequinone 8. 0.000 6,0.865+0,021 32,0.894+0.008 cis-Acenaphthene-1,2-diol 0,000 4, 0.854+0.012 7, 0.570+0.033 trans-Acenaphthene-1,2-diol 0.000 3,0.861+0.024 16^,272+0,014 cis -Acenaphthene-1.2-diol 2, 0.883+0.005 4., 0.933+ 0.021 40, 0.961+0.007 dinitrate trans-Acenaphthene-1.2-diol 3, 0.931+ 0.013 2,0.938+0.033 40,0.961+0.008 dinitrate - 126 -R E F E R E N C E S - 127 -( 1 ) Gray, P., and Hayward, L» D., The Chemistry of the Nitrate Esters, in preparation. ( 2 ) Honeyman, J., and Morgan, J. W. W,, Adv. Carbohydrate Chem. 12 117 ( 1 9 5 7 ) , ( 3 ) Boschan, R., Merrow, R. T., and Vandolah, R. W., Chem. Rev. 55 485 ( 1 9 5 5 ) . 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