University of Southern California Dissertations and Theses

Syntheses of fluoranthene derivatives with substituents in the 2-position

(USC Thesis Other)

Syntheses of fluoranthene derivatives with substituents in the 2-position

PDF

Download

Open document

Flip pages

Download a page range

Download transcript

Copy asset link

Request this asset

Transcript (if available)

Content SYNTHESES OP FLUORANTHENE DERIVATIVES WITH SUBSTITUENTS IN THE 2-POSITION A Thesis Presented to the Faculty of the Department of Chemistry The University of Southern California In Partial Fulfillment of the Requirements for the Degree Master of Science in Chemistry by John Hans Menkes February 1951 UMI Num ber: EP41588 All rights reserved INFO RM A TIO N TO ALL U SER S The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI' Dissertation Publishing UMI EP41588 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 8 1 0 6 -1 3 4 6 This thesis, written by JolmJBan&Jltenkes.................................. under the guidance of Faculty Com m ittee, and approved by a ll its members, has been presented to and accepted by the Council on G raduate Study and Research in p a rtial fu lfill ment of the requirements fo r the degree of Faculty Committee s f c r .. Chairman TABUS OF CONTENTS PAGE INTRODUCTION ...................................... 1 Historical ............................. 1 Fluoranthene Derivatives Obtained Directly from Fluoranthene ......... ............... 5 Fluoranthene Derivatives Obtained by Synthesis of the Fluoranthene Nucleus ............. 11 DISCUSSION OF PROBLEM .............. 18 DISCUSSION OF RESULTS . . . ..................... 21 Preparation of 3-Aminofluoranthene............. 21 Preparation of 2-Bromofluoranthene ............. 23 Proof of Structure of 2-Broroofluoranthene .... 28 Reactions of 2-Bromofluoranthene............. . 31 EXPERIMENTAL .......... 32 SUMMARY........................... 49 BIBLIOGRAPHY...................................... 51 A C K N O W L E D G M E N T The author is indebted to Dr. M. C. Kloetzel for his long and patient guidance in this inve stigation. INTRODUCTION Historical The commercial availability of the aromatic hydro carbon fluoranthene allows it to become a potential starting material for the synthesis of polycyclic compounds. How ever, despite the fact that more than seventy years have elapsed since its discovery, very little is known about the fundamental chemistry of the compound, and its true struc ture has only been known since 1930. Fluoranthene was first isolated by Goldschmiedt (1), who obtained It by distillation of mercury ores in the absence of air. An erroneous analysis of the hydrocarbon showed it to have the formula O^H^, and Goldschmiedt thereupon proposed structure I for the compound, which he named Idryl. I That same year Fittlg and Gebhard (2) isolated fluoranthene from coaltar, where it was found mixed with pyrene. These authors also gave for the empirical 15 10 formula, and upon oxidation of the hydrocarbon obtained an acid, melting at I9I-I920, which had the formula C^H^O^. 2 Distillation of that acid with zinc dust formed fluorene almost quantitatively, while decarboxylation produced fluorenone. The structure of the fluorenone carboxylie acid was further shown by Fittig (3# to be II through the following series of reactions: II From the above evidence Fittig proposed III as the structure of fluoranthene. •H c =-c.H o coon (showing o- posltlon of one COQH) COOH C jOOH COOH o coOH (showing im position of other COOH) III At that time Goldschmiedt (5, 6, 7) attempted to 3 prepare various derivatives of fluoranthene without too much success♦ Upon chlorinating the hydrocarbon, a high- melting trichloro compound was obtained. Bromination yielded a tribrorao product, and two other compounds, melting at 112-114° and 205°, respectively, the structure of none of which was established. The sulfonic acid which Goldschmiedt prepared could not be purified, and heating the latter with potassium cyanide gave various oils, from which a compound melting at about 220° was isolated after prolonged purification. Its structure was uncertain. No further work was done in this field, and structure III was generally accepted, until Graebe (8) and Mayer (9) attempted to prepare fluoranthene synthetically. They found that treatment of 9-ethylfluorene at high temperatures failed to yield fluoranthene, but instead a mixture of IV and V was Isolated by Mayer, and phenanthrene was obtained by Graebe. CH=CHa 71 V PbO x A IV Furthermore, neither fluoreneacetic nor fluorene- 4 propionic acid could be transformed into a fluoranthene derivative. Von Braun and Reutter (10) then found that compound VI could not be forced to undergo ring closure. VII and VIII, however, cyclized with ease. VI VII VIII from this evidence it became apparent that two five- membered rings attached to the same benzene nucleus in the fashion of III would Involve much strain. Therefore, fluoranthene, if structure III were correct, would be quite hard to synthesize. However, using 9-fluorenepropionyl chloride (IX) as starting material, von Braun and Anton (11) easily prepared fluoranthene by the following series of steps: o 5 Thus it was shown that X was the true structure of fluoranthene, and that the empirical formula was instead of the previously accepted C,_H . ip 10 Using this structure as the basis for further research, von Braun began a systematic investigation of the reactions of fluoranthene. Fluoranthene Derivatives Obtained Directly from Fluoranthene The reduction of fluoranthene was first examined by Goldschmiedt (5)* Using sodium amalgam and hydrogen iodide (5), sodium amalgam (13)* or sodium (12), 1,2,3,lOb-tetra- hydrofluoranthene(XI )can be prepared from fluoranthene. Von Braun (13) showed that hydrogenation of fluoranthene would form tetrahydro- (XI), dekahydro- (XII), and perhydro- fluoranthene (XIII) successively, depending upon the amount of hydrogen which was allowed to react with the unsaturated hydrocarbon. No hexahydro- or dihydrofluoranthenes were found. XI XII XIII Bromination of fluoranthene was first attempted by 6 Fittig and Gebhard (3), who were able to obtain only a dlbromo derivative melting at 204-205°, whose structure is still uncertain. Tobler et al. (14) believed this compound to be 3,8-dibromofluoranthene (XIV) on the basis of the following evidence. B v ' XIV Since raonobromination yields 3-bromofluoranthene, one bromine is surely in that position. Dibromination of tetrahydrofluoranthene (XI) gave a compound in which both bromines were aromatic. This derivative gave upon dehydro genation the dibromofluoranthene melting at 205° « ■ Therefore, the second bromine Is not in the 4,5, or 6 position. Of the six other positions left, the 8-position is most reactive in other substitution reactions, and therefore most likely to be attacked. Using less drastic conditions for bromination, von Braun and Manz (15) obtained a monobromo derivative, which melted at 103°. Von Braun et al. demonstrated that bromination, nitration and sulfonation Involved the same position on fluoranthene. The interrelationship of the 7 monosubstitution products was demonstrated (15) as follows, (P = fluoranthyl radical.) P— COOH / ^ NaOH NaCN P— SO_H 3 NaOH s/ F— OH XV HoO ■ m S S m CISO3H NH3 HC1 dil 230° P— H F— CN Br* Cu2{CN)2 P— Br CS F- SnCl, ± P— NHr The actual position of the substituents was proved when sodium amalgam reduction of XV and XVI yielded the two isomers XVII and XVIII, which were converted to the Identical urethane derivative XIX. OH XV OH < 6 i » H , 05T XIX * NCO synthesis -A XVII m.p, 136-139° XVIII m.p. 130-1340 8 Confirmatory evidence was obtained from the following reaction sequence. Nqo » C r ^ 7 hi\ c_ 40° vt.o HaO V N . H* ? CC^lCOOH NHcoch, a lactam The structure of 1,2-dicarboxy-9-fluorenone (XX), which was obtained from 3-fluoranthoic acid (XXI) was proved by the following sequence (16). O CMaCH^coon O COOH COOH coon y / Thus, bromination, nitration and sulfonation, under mild conditions, form mainly 3-substitution products. 9 However, other isomers which are produced at the same time, and of which only the 8-derivatives could be shown to be of each individual isomer an arduous task. Tobler et al. (14) prepared 3-bromofluoranthene from fluoranthene in 48$ over-all yield by chloranil dehydro genation of 1,2,3,lQb-tetrahydro-4-bromofluoranthene, and were able to improve von Braun's yield (15$) of 3-bromo- fluoranthene obtained by direct bromination of the hydro carbon. Catsiff (l?) attempted to brominate fluoranthene using M-bromosucciniraide, but without success. Fluoranthene reacts with oxalyl chloride, benzoyl chloride and phthalie anhydride in the Friedel-Crafts reaction. Von Braun (16) showed that in all three cases two isomers are formed. The major product was shown to be the 8-derivative from the following series of reactions. present complicate the reactions and make isolation other, uniden tified acid XXII Co] XXV V c o o c r t i «> C O O C . H 3 * o o° 1 XXIII XXIV Compound XXIII was already known (18). This and the fact that XXII gave two oxidation products, XXIV and XXV, indicated that the substituent was either in the 7- or* 8- posltion. Ring closure of o-(8-fluoranthoyl)benzoic acid (XXVI) should give two isomers, XXVII and XXVIII, while the 7-isomer would only give one product, XXVIII, after ring closure. Both XXIX and another unidentified compound probably XXX, were isolated after oxidation and decarboxyl ation of the cyellzation products of XXVI. This showed that in XXVI the 8-position was substituted. COOH XXIX XXVI XXVII XXVIII XXX The side product was the 3-substituted derivative as was shown by these transformations. (F = fluoranthyl radical.) 11 N-OH p > 1 1 F - C — M o The characteristic 3- and 8-substitution of fluoranthene is exhibited in other Frfedel-Crafts reactions. Thus, acetyl chloride reacts with fluoranthene to produce 3- and 8-acetyIfluoranthene and a diacetyl derivative. While apparently all three of these compounds were obtained by Campbell and Easton (19), Buu-Hol and Cagniant (20) only isolated what is probably the impure 8-isomer. However, the identity of 8-acetylfluoranthene has not been shown rigorously by either group of authors. Addition of tert. butyl chloride (21), trlchloro- methyl cyanide (19), oxalyl chloride (16, 19), and aminoformyl chloride (22) to fluoranthene have been studied and have all been shown to yield the expected derivatives. Fluoranthene Derivatives Obtained by Synthesis of the Fluoranthene Nucleus Since von Braun (10) first synthesized fluoranthene, the hydrocarbon has been prepared by numerous other methods. 12 Cook (23) was able to prepare It in small quantities by the following steps. CH; OH CH. A1CI ■tfSa Later Orehin (24) used an adaptation of the above synthesis, and made cyclohexanone and 1-bromonaphthalene his starting materials. MgB’ f oh This process, however, requires high temperatures and derivatives in which the location of the substituent is 13 known, for certainty cannot well be made. Therefore, Bergmann (25) devised the following synthesis. H C - c f || V C u c U . r n . e t K Y \ HC) XXXI Starting with 1-fluoranthoic acid (XXXI), prepared in the aforementioned series of steps, l~arainofluoranthene could be obtained with fair ease. Several of the other described syntheses of fluoranthene employ condensations of the Diels-Alder type. The synthesis of Campbell and Gow involves the following sequence (26). 14 3-Bromofluoranthene and 7,10-dimethylfluoranthene were also synthesized in this manner. Aceeyelone (XXXII) is the starting material in the synthesis of 7,10-diphenyl-8,9-dicarboxyfluoranthene (27), and J,lG-dlphenyl-8-benzoylfluoranthene (28). XXXII Mertel (29) condensed acenaphthylene with various dienes such as isoprene, butadiene, and 2,3-dimethyl- butadiene to obtain fluoranthene derivatives. The condensation of acenaphthylene and 2,3-dimethylbutadlene proceeded as is shown in the following reaction. 15 9-Alkyl-9-fluorenols have been employed as starting materials in a novel adaptation of the Dlels-Alder conden- sation to yield fluoranthene-2,3-dicarboxylic acid anhydride and 1-methylfluoranthene (30). The Michael reaction has been used repeatedly for the preparation of fluoranthene derivatives. For example, Tucker (31) prepared 1-methyIfluoranthene through conden sation of 9-carboethoxyfluorenone and crotononitrile, with subsequent cyelizatlon. tAeinyl ftDgenclt i O kOH cMaU4 o iTOCI, H^O H,C'c hCK3C.OO u KOH ^ ' A 5nCl* 16 1,3-Dimethyl fluoranthene was also synthesized by this method (32). The Pschorr type of condensation may be used on derivatives of 1-phenylnaphthalene in the following manner (32). This method has been used to prepare thylfluoranthene, 8-methylfluoranthene, 1,2,3**trimethylfluoranthene and ethyl fluoranthene-8-carboxylate (33> 3^0). Finally the Grignard reaction has been employed successfully for the synthesis of alkylfluoranthenes (3^)* NaNOa ■ I [Hj h<jB ' CHj O + CHj- C=cH-c.-Ch3 o 1 I I IT 1-Phenyl-3-methylfluoranthene and. 1,3-diphenyl- fluoranthene were made using fluoreny1lithium as starting material (35) • DISCUSSION OF PROBLEM From the literature review previously presented, it becomes evident that although the direct attack of reagents on the fluoranthene nucleus only produces the 3- or 8-isomers in any amount which makes them practicable to be isolated, some substituents in other positions may be Introduced easily during the synthesis of the fluoranthene nucleus itself. By these two types of methods monosubsti tution products in all except the 2-position have been conclusively synthesized. A patent by Bergdolt and Ballauf (36) describes the preparation of what is apparently a mixture of 2- and 3-hydroxyfluoranthenes. No proof of structure for these two compounds and no further data are given by these authors. Campbell and Wang (30) prepared 2-carboxyfluoranthene from fluoranthene-2,3-dicarboxylic anhydride. The product, however, was obtained in yields of less than 1$, starting with 9-, hydroxy-9-methylfluorene, and could not be obtained analytically pure. The Friedel-Crafts reaction of 3-amlnofluoranthene with phthallic anhydride, which might be expected to result in 2-substitution, yielded instead 3-amino~8-(2-carboxy- benzoyl)fluoranthene (37). 19 NH*. CHa-COOCO Nd.C| AICI3 iao° NHa. Meyer and Falta (38) have described bromination of 3-aminofluoranthene, but no further details about the compound produced are available. Thus, a method of synthesis for 2-fluoranthyl derivatives had still to be accomplished. The work herein described had as its goal the introduction of a bromine atom in the 2-position of fluoranthene by utilization of the ortho directing influence of an amino group in the 3-position. Subsequent removal of the directing group should leave 2-bromofluoranthene, which could then be used further to prepare other 2-fluoranthyl derivatives. 20 It was also necessary to establish the identity of the 2-bromofluoranthene. This could best be done by oxidation and decarboxylation. To make this a practical method for the preparation of 2-fluoranthyl derivatives, It appeared necessary to Improve the known method for obtaining 3~nltrofluoranthene from which in turn the 3-amino fluo ran thene was to be prepared. Previously von Braun had reported his yield of 3-nitrofluoranthene to be in the neighborhood of 10-15# (l6). It appeared possible to adapt Tobler*s method for the synthesis of 3-hromofluoranthene (1^) with advantage for the synthesis of 3-nltrofluoranthene: DISCUSSION OF RESULTS Preparation of 3-Aminofluoranthene 3-Aminofluoranthene (III) was prepared by the cata lytic reduction of 3-nltrofluoranthene (II) which, in turn, was obtained by the direct nitration of fluoranthene. I II III When nitration of fluoranthene was run according to directions given by von Braun and Manz (15), yields were poor, since side products, such as high-melting nltro compounds and acids, were also formed. But when the reaction was run at 65°, Instead of at 95° as was done by von Braun, the main products were 3-nitrofluoranthene and 8-nitrofluoranthene. From this mixture the former compound was obtained pure in 50$ yield. S-Nitrofluoranthene, which up to this time had never been isolated, was identified by conversion to 8-acetylamlnofluoranthene, which had previously been obtained by Buu-Hoi and Cagniant (20) through the following series of steps. 22 n 0 - M o An attempt to adapt the method of Tobler et al. (14) for the preparation of 3-bromofluoranthene, to the synthesis of 3-nltrofluoranthene, failed since nitration of 1,2,3,lOb-tetrahydrofluoranthene (IV) did not give satisfactory yields of what was probably the expected 4-nitro-l,2,3#lOb-tetrahydrofluoranthene (V). HN03 HPk. IV V When reduction of 3-nltrofluoranthene was carried out catalytlcally, excellent yields of the pure 3-amino- fluoranthene (III) were obtained. Reduction with stannous chloride according to the method of von Braun and Manz (15) was less desirable, for the amine, as obtained from this reaction mixture, was not too pure. Preparation of 2->BroiBof luoranthene 23 3-*Aminofluoranthene (III) was acetylated with acetic o anhydride at 50 to form 3-acetylaminofluoranthene (VI). When the acetylation was run at 90° and a trace of sulfuric acid was added, 3-^lacetylaminofluoranthene (VII) was formed in good yield. nh III VI 90° VII Von Braun and Manz (15) have only prepared 3-acetyl- aminofluoranthene (VI). The structure of 3-diaeetylamino- fluoranthene (VII) was proved by hydrolysis of the compound to form both VI and III. 1 5 nNHCOCH3 K J (C O C M 3 ') I I I 24 Dlacetylation is fairly common when dealing with hydrocarbons of large molecular weight, whose amines are weakly basic. For example, 9-dIaeetylamInoanthracene (39)* 2-diacetylaminochrysene (40), and 5-diacetylamino- acenaphthene (41) have been prepared with ease from their respective amines. Bromination of 3-acetylaminofluoranthene (71) in acetic acid produced 2-bromo-3-acetylaminofluoranthene (VIII) in good yields, if the temperature of the reaction o o was kept below 50 . At reaction temperatures of 75 or higher, 2-bromo-3-dlaeetylaminofluoranthene (IX) is formed exclusively, while mixtures of the two bromo derivatives (VIII and IX) are obtained when bromination is run between 50° and 75°. NHC-OCM VI VIII IX A reaction analogous to the aforementioned one has been shown to occur (42). The structure of IX was proved by hydrolysis of the compound to VIII and to 2-bromo-3-*amInof luoranthene (X). Bromination of 3-diacetylaminofluoranthene (VII) also produced IX. Bv- IX VIII VII XI Both VIII and IX may be hydrolyzed using either base or acid catalyst. In the former case the amine (X) is isolated, while in the latter Instance both the amine sulfate (XI) and what Is probably the amine acid sulfate 2 6 may be found. The yield on this step is good, but the amine and the amine salts formed are unstable and decompose when exposed to light or air and upon recrystallization from absolute alcohol. One possible decomposition reaction may be analogous to the one found by Pschorr and Schroter for 1-aminoanthracene (43) • H I ^ \ OOfS + w n < f A c - Diazotizatlon of XI in sulfuric acid and reduction of the diazoniura salt (XII) with hypophosphorous acid gave 2-bromofluoranthene (XIII). The yields of the purified bromo compound were very low, due to impurities which were associated with the desired produet and which could only be removed by high vacuum sublimation or repeated crystalli zations and fractional adsorption of the mixture upon alumina. XI + H3po3 + r \ l a + H i . s c x Diazotizatlon of polycyclic amines has been carried 27 out with varied success by other authors, Ullmann and Conzetti (44) were able to obtain 1-hydroxyanthraquinone from 1-aminoanthraquinone in 95$ yield. O NaHS04 U o OH Sehaarsehmidt (45), on the other hand, was unable to diazotize 1-amino-2-bromoanthraquinone. Instead of the expected diazonium salt, N-nitro so-1-amino-2-bromoanthra- quinone was obtained. H a SO^j. JL 1 H N-NO _B r The same author also found that conversion of 2-amino- anthraquinone into 2-haloanthraquinone was only effected in 20$ yields. Pisovschi (46) found the following abnormal diazotization to occur with 1-aminoanthracene. When the diazotizatlon of X was run in hydrochloric acid, a high melting nitrogen containing compound was isolated, which may possibly be XVT, a reduction product of XV, which is analogous to XIV. The structure of 2-bromofluoranthene (XIII) was proved by oxidation and subsequent decarboxylation of the acids formed. Oxidation of 2-bromofluoranthene gave 3-bromo-9-fluorenone-l-carboxylic acid (XIX), a previously unknown compound, and 9-fluorenone-l-carboxylic acid (XVII). Compound XIX was identified by decarboxylation to H H N — N Br XV XVI Proof of Structure of 2-Bromofluoranthene 29 3-bromo-9-fluorenone (XX), which hah previously been prepared (47). The melting point of the 3-bromo-9-fluorenone obtained by decarboxylation of 3-broma-9-fluorenone-l- carboxylic acid was I58-I600. A mixed melting point with a sample of 3-bromo-9-fluorenone, melting at 259-160° and synthesized according to the method of Miller and Bachmann (47), showed no depression. TABLE OF MELTING POINTS OF ISOMERIC BROMO-9-FLUGRENGNES 1-bromo-9-fluorenone 134-135° Huntress (48) 2-brorao-9-fluorenone 149-150° Courtot and Vlgnatl (49) 3-bromo-9-fluorenone 161-162° Miller and Bachmann (47) 4-bromo-9-fluorenone 125-126° 190-191°* Huntress (48), France (60) Miller and Bachmann (47) ♦This melting point has been questioned by Huntress et al. (48) ----- Reduction of 3-bromo-9-fluorenone (XX) gave 3-bromo- 9-fluorenol (XXI). 9-Fluorenone-l-earboxylic acid (XVII) was Identified by comparison of its melting point with an authentic sample obtained by oxidation of fluoranthene, and by decarboxylating it to 9-fluorenone (XVIII). O coon c«co CllCO. O COOH CuCO' XXIV XXV 8-Bromofluoranthene (XXII) would upon oxidation form 6-bromo-9-fluorenone-l-carboxylIc acid (XXIII), which would, upon decarboxylation, yield 3-b**omo-9-fluorenone (XX), but, Instead of forming compound XVII, 7-bromo-9-fluorenone-1- carboxylic acid (XXIV) would be produced, which, upon decarboxylation, yields 2-bromofluorenone (XXV). 31 Reactions of 2**Bromofluoranthene Treatment of 2«bromofluoranthene with cuprous cyanide in pyridine, according to the method advocated by Newman (51), gave 2-cyanofluoranthene (XXVI), which upon hydrolysis with sodium hydroxide and hydrogen peroxide, using the method of Noller (52), produced 2-acetamidofluoranthene (XXVII), which of course differed from the known 8~acetamidofluoranthene (16). Attempts at forming a magnesium Grignard compound with 2-bromofluoranthene were unsuccessful, even though heat was used in an attempt to force the reaction. This would confirm similar observations on 3-*bromofluoranthene by von Braun and Mans (15) and Catsiff (17)* CONN XXVI XXVII EXPERIMENTAL Nitration of Fluoranthene .- Unrecrystalllzred fluor anthene (400 g.) was dissolved in glacial acetic acid (2.5 1.) and the mixture was heated to about 85° to effect complete solution. Before the addition of nitric acid was commenced, the reaction flask was cooled to 65°. Concen trated nitric acid {196 cc.) dissolved in an equal amount of glacial acetic acid was added dropwise over the course of six hours, while the reaction temperature was being maintained below 70° at all times. The solution changed color from dark green to red, and finally a fine yellow precipitate began to separate. After addition of the nitric acid was completed, the mixture was heated at 65° for two more hours, and then filtered while still at a temperature of 60-65°. The precipitate, 3-nltrofluoranthene (II), was dried overnight. Yield, 240 g. (50$); m.p. I53-1560* The product was recrystallized from glacial acetic acid, and was obtained as fine orange needles melting at 158-159°. (Reported 159-160°) (X5)- The filtrate from which 3-nitrofluoranthene had separated was cooled to 4-0°, filtered, and then allowed to stand at room temperature overnight. Pale yellow crystals of 8-nltrofluoranthene were removed. Yield, 27 g. (5.5$)J m.p. 130-135°. Several recrystallizations produced an 33 analytical sample melting at 130-131.5°. Calcd. for G.^H OH: M, 5.67# 16 9 2 Pound: N, 5-53# The structure of the aforementioned compound was proved by conversion to the known 8~acetylaminofluoranthene ( 16) . 8-Nitrofluoranthene (5.0 g.) was suspended in absolute alcohol (150 ce„) and platinum oxide (0.2 g.) was added. The solution was subjected to a 40 lbs. pressure of hydrogen, until there was no further absorption of gas. The catalyst was filtered off, and the alcohol evaporated under reduced pressure. Yellow crystals of 8-amino- fluoranthene, m.p. 150-158 (dec.), were obtained. (Reported m.p. 168-169°) (16). The 8-aminofluoranthene thus formed was treated with acetic anhydride (15 cc.) and acetic acid (15 ce.). Two drops of concentrated sulfuric acid were added to eatalyze the reaction. The mixture was warmed to 60°, filtered hot, and poured into cold water. The 8-acetylaminofluoranthene which settled was collected, and reerystallized with charcoal from absolute alcohol; m.p. was 190-193°• (Reported 191°) (16). Attempted Nitration of 1,2,3,10b-Tetrahydro- fluoranthene (IV).- 1,2,3,lOb-Tetrahydrofluoranthene 3* (10 g.), m.p. 71-73 > prepared according to the method of Tobler et al. (14), was dissolved in glacial acetic acid (90 cc.). Concentrated nitric acid (4.1 cc.) in the same amount of glacial acetic acid was added dropwise for half an hour, the temperature being kept at 60° during the whole course of addition. Finally sulfuric acid (1 cc.) was added. The solution was warmed to initiate the reaction, which was then allowed to continue for four hours. The acetic acid solution was then evaporated to 15 cc., water (250 cc.) was added, the turbid solution was shaken with methylene chloride (100 cc.) to extract any organic material, and the methylene chloride solution was extracted with 10$ sodium carbonate. The carbonate took up much color, indicating the presence of large quantities of acid material. Finally the methylene chloride solution was dried with calcium chloride, and filtered twice through charcoal. Upon evaporation of the methylene chloride a red oil was formed, which was dissolved in hot glacial acetic acid, poured into a beaker of ice, and allowed to stand. Yellow crystals (possibly 4-nitro-l,2,3»lOb-tetrahydro- fluoranthene) were formed, which were dried and recrystal lized from toluene and petroleum ether. Melting point, 49-53°; weight, 0.3 g. (6$). When nitration of 1,2,3,lOb-tetrahydrofluoranthene was carried out at more drastic conditions, a brick red 35 compound, m.p. 217-218 , and yellow crystals decomposing o above 270 were obtained. Their nature is unknown. Dehydrogenation of the nitration product, melting point 49-53°t failed to yield any definite products, and only tars could be Isolated. 3-Aminofluoranthene (III). (a.). Chemical Reduction of 3-Nltrofluoranthene.- Reduction of 3-i*ltrofluoranthene with stannous chloride was carried out according to the directions of von Braun and Manz (15). 3-Nltrofluoranthene (1.2 g.), melting point I53-I560, was dissolved in glacial acetic acid. Concentrated hydrochloric acid (10 cc.) and stannous chloride (8.4 g.) were added. A precipitate formed, and upon the addition of excess base, the stannic salts went into solution, leaving the amine precipitated. The amine was dissolved in methylene chloride, and was precipitated as the blue-green hydrochloride upon addition of an ethereal solution of hydrogen chloride gas. Weight of 3-amlnofluoranthene hydrochloride, 1.2 g, (96#). (b), Catalytic Reduction of 3*Nltrofluoranthene.- 3-Nitrofluoranthene (20 g.), m.p. 158-159°* was suspended in ethanol (150 cc.), platinum oxide (0.25 S*) was added, and the suspension was subjected to a pressure of 40 lbs. of hydrogen until no further absorption of gas occurred. This took place within two to three hours, depending upon 36 the particle size of the nitro compound. 3-Amlnofluoran- thene precipitated in green-yellow needles. Yield, 14 g. (80$); m.p. 110-111°. (Reported 111°) (15). By evaporation of the alcohol solution under reduced pressure, the aforementioned yield was increased by about two more grams. 3-Acetylaminofluoranthene (VI).- 3-Aminofluoranthene (42 g.) was suspended in glacial acetic acid (200 cc.). Acetic anhydride (30 cc.) was added, and the temperature of the mixture was allowed to rise to 50°» at which point it was kept for an hour by means of a steam bath. The solution was then cooled to 10° and filtered. Pale yellow crystals of 3-acetylaminofluoranthene were obtained. Yield, 48 g. (96$); m.p. 243-244°. Recrystallization from absolute alcohol gave pale yellow needles, m.p. 246-247°. (Reported 241°) (15). 3-Dlacetylaminofluoranthene (VII).- 3-Amino- fluoranthene (4.5 g.) was dissolved in acetic anhydride (150 cc.), a few drops of concentrated sulfuric acid were added, and the solution brought to a boil for a minute. The acetic anhydride was decomposed with water, the precipitate was filtered off, and recrystallized from absolute ethanol. White needles of 3-diacetylamlnofluoranthene were obtained. Yield, 2.7 g.; m.p. 168-169°. 37 Found: Calcd. for C^fiLcN0o: du Ap d C, 78.87$; H, 5.22$; N, 4.84$6 C, 79.30$; H, 5•00$; N, 4.72$ The diacetylaiQlne is more soluble in alcohol, and its solutions have a less noticeable blue fluorescence than the monoacetyl compound. 3-Diaeetylaminofluoranthene may also be obtained by heating a solution of 3^acetylaminofluoran thene in acetic anhydride, and precipitating the product by the addition of water. 3-Diacetylarainofluoranthene was hydrolyzed by dissolving it (0.2 g.) in absolute alcohol (10 cc.), adding 20$ sodium hydroxide (5 cc.) and refluxing the solution for an hour. The precipitate which settled upon cooling was filtered off and recrystallized from benzene and petroleum ether. Melting point of crystals was 240-241°. A mixed melting point with authentic 3-acetylamlnofluoranthene showed no depression. The mother liquor which possessed the green fluorescence of amlnofluoranthenes was evaporated. Green-yellow needles of 3-aralnofluoranthene, melting at 108-109°, were obtained, which did not depress the melting point of authentic 3-aminofluoranthene. Bromination of 3-*Ace tylaminof luoranthene. (a). 2-Bromo-3-acetylaminofluoranthene (VIII).- 3-Acetylamino- fluoranthene (6.0 g.) was dissolved in warm glacial acetic acid (180 cc.). The solution was cooled to 45°, and 38 bromine (1.45 cc* or 1.2 moles per mole of 3»acetylamino~ fluoranthene) was added dropwise. The solution was allowed to stand until there was no further evolution of hydrogen bromide, the orange precipitate was filtered off, washed several times with dilute acetic acid, and washed subsequently with a 15$ solution of sodium bisulfite. The mother liquor was poured into an excess of water, the precipitate which formed was removed, and then added to the material originally precipitated. The combined weight of unrecrystallized material was 6.2 g. The impure 2*»bromo- 3-acetylaminofluoranthene was recrystallized from bromobenzene, yielding 4.2 g. of orange needles melting at 265-268°. After further purification, the melting point of the compound rose to 271-272°. Calcd. for C 0H ONBr: C, 63*93$; H, 3*58$ lo 12 Found: C, 63*96$; H, 3*68$ (b). 2-Bromo-3-dlacetylaminofluoranthene (IX).- 3- Acetylaminofluoranthene (48 g., 0.18 moles) was added to glacial acetic acid (2 1.). Solution was effected by heating the mixture to 65°, and bromine (12 cc., 0.23 moles) was slowly added to the solution over the course of two hours. After the reaction was completed, the mixture was heated to 95° for 15 minutes. The precipitate which formed was filtered off from the cooled solution, washed with 39 dilute acetic acid and sodium bisulfite, suspended in water, and filtered again. It was dried overnight. Yield, 53 g. (97#); m.p. 210-214°. After several recrystallizations from bromobenzene, pale yellow needles melting at 215-216° were obtained. Calcd. for C20Hl40gKBr: C, 63.18#; H, 3.71# Found: C, 6 3 . 3 9 H, 3-91# Bromination of 3-<ii&eetylaminofluoranthene (1 g.) in acetic acid (30 cc.) with bromine (0.25 cc.) yielded 2-bromo-3^dlacetylaminofluoranthene, m.p. 210-212°. A mixed melting point with 2-bromo-3-diaeetylaminofluoranthene, prepared by bromination of 3-acetylaminofluoranthene, did not show any depression. 2-Bromo-3-diacetylaminofluoranthene (33 g«) was dissolved in dloxan (300 cc.) and alcohol (500 cc.) and hydrolyzed with sulfuric acid (20 cc. of concentrated sulfuric acid in 80 cc. water). The solution was heated at reflux for two hours, and the precipitate which formed was filtered off. After several recrystallizations from alcohol and bromobenzene, the melting point of the compound Isolated was 263-264°. A mixed melting point with authentic 2-bromo-3-acetylaminofluoranthene showed no depression. The mother liquor from this hydrolysis contained 2-bromo-3- amlnofluoranthene. 40 2-Bromo-3-aminofluoranthene Sulfate (XI). - 2«-Bromo- 3-diacetylaminofluoranthene (10 g.) was dissolved in alcohol (550 cc*) and dioxan (150 cc.). Dilute sulfuric acid (20 cc. of the concentrated sulfuric acid in 90 cc. water) was added, and the solution was refluxed for 3 hours. The solution became at first Intensely blue fluorescent, and then assumed a green fluorescence. The precipitate which formed, and which probably was 2-bromo-3-amino- fluoranthene acid sulfate, was filtered off. Yield, 3.3 g. (32$); m.p. above 285°. Treatment of the aforementioned compound with warm 6 N.potassium hydroxide produced-what was probably 2-bromo- 3-aminofluoranthene (X), m.p. 115-125° (dec.). The volume of the filtrate was reduced to 100 cc. by distillation of the solvents at 60° and 30 mm. Upon cooling, pale yellow crystals of 2-bromo-3-aminofluoranthene sulfate separated from the liquid. Yield, 4.8 g. (55#)j m.p. 190-205° (dec.). Calcd. for (C^H^NBr^SO^: C, 55.66%; H, 3.21# Pound: C, 55.50#; H, 3-76# The amine sulfate was soluble in ethanol and acetone, forming greenish fluorescent solutions. It was unstable to light and air, and decomposed upon drying In air, or upon recrystallization at higher temperatures, to form a 41 green-yellow solid, which, when recrystallized, melted at 238-239°• The exact nature of this substance was not determined, but a possibility (XVI) has been mentioned in the Discussion section of this study. Calcd. for C H NBr: C, 66.80$; H, 2.98$ d* 17 Found: C, 66.6i$; H, 3-37$ Treatment of 2-bromo-3-amlnofluoranthene sulfate with warm water produced a compound melting at 111-121°, and which probably was 2-bromo-3-aminofluoranthene. 2-Bromofluoranthene (XIII).- For the preparation of 2-bromofluoranthene, the following procedure, avoiding isolation of the unstable 2-bromo-3-aminofluoranthene sulfate, was adopted. The solution of 3-amino-2-bromo- fluoranthene sulfate, after completion of the hydrolysis of 10 g. of 2-bromo-3-diacetylaminofluoranthene, was filtered. The filtrate was evaporated at 60° under reduced pressure until It became .cloudy, filtered again, and cooled. The precipitate which settled, and which was 2-bromo-3- aminofluoranthene sulfate, was centrifuged off. The mother liquor was diluted with twice its volume of water, and centrifuged at 2000 r.p.m. for 30 minutes. The two precipitates were combined. Sulfuric acid (30 cc. of the concentrated acid In 15 cc. water) was added to the ice-cold « solution with stirring, never allowing the temperature of 42 the solution to rise above 3°. A solution of sodium nitrite (2.2 g. in 10 cc. water) was added drop by drop. The reaction mixture turned dark, and most of the solid material entered solution. Half an hour after addition of -the sodium nitrite had been complete, pre-cooled 30$ hypophosphorous acid (200 cc.) was added slowly. The solution was stirred for four hours at 0°, and put into the ice box until evolution of nitrogen had ceased. This usually required three to four days. The precipitate which settled from the solution, which by that time was almost colorless, was filtered off, dried, and extracted several times with ether (six 100 cc. portions of solvent). The ether solution was washed with water and 10$ sodium carbonate, dried with sodium sulfate, and passed through a 30 cm. alumina adsorption column. Most of the 2-bromofluoranthene passed through the column with the solvent, but the lowest, pale yellow band, also contained some of the desired product. This band was therefore eluted with ether, and the solution combined with the solution which had already traversed the column.. The ether was evaporated, and the residual solids were twice recrystallized from alcohol, using charcoal. Yield of 2-bromofluoranthene, 1.0 g. (22$); m.p. 111-113°. After recrystallizing the compound several more times from alcohol, pale yellow needles, melting at 114-115°* were 43 obtained. Calcd. for C.^H-Br: 16 9 Pound: C, 68.34#; H, 3.22# C, 68.40#; H, 3.21# From the mother liquors a compound could be Isolated, which upon recrystallization gave greenish-white needles, melting at 90.0-90.5°• The nature of this product was not determined. When diazotizatlon of the 2-bromo-3-aminofluoran~ thene (X) was effected in hydrochloric acid, a nitrogen- containing compound, melting at 225-226°, was obtained. Its nature has been commented upon in the Discussion. When the reduction of the diazonium salt was carried out with alcohol and copper according to the method of Ullmann and Eiser (53), the yield was less than 1#. Preparation of 2-bromofluoranthene-3-dlazonium sulfate in pyridine sulfate and sulfuric acid according to the method of DeBUlt and VanZandt (54) failed to improve the yield, since a large amount of a dark red dye, probably a diazo compound, was formed in the process. Found: G, 75-30#; H, 4.14# Found: Calcd. for C__H N BrCl: 32 21 3 C, 68.32#; H, 3.75# G, 69.04#; H, 4.08# 44 2-Cyanofluoranthene (XXVI).- 2-Bromofluoranthene, m.p, 111-113° (220 mg.), was mixed, with cuprous cyanide (84 mg.). The mixture was wetted with dry pyridine (0.1 cc.) and heated at 210° for 20 hours. The solution was then cooled, and the solid mass washed into dilute ammonium hydroxide (5 cc. of concentrated ammonium hydroxide in 5 cc. water). The ammoniacal solution was extracted with benzene (35 cc.) and filtered through a sintered glass funnel. The residue was extracted several times with benzene, and the two portions of extracts were combined. The organic layer was separated, and washed four times with 10 cc. portions of dilute ammonium hydroxide, twice with dilute hydrochloric acid, and twice with water. The benzene solution was dried and evaporated, 2-Cyanofluoranthene melting at 128-133° was obtained. Yield, 120 mg. (88$). Several recrystallizations from ethanol produced an analytical sample melting at 136-137°• Calcd. for C H N: C, 89.85$; H, 3-99$ i . ( y Pound: C, 89.86$; H, 4,22$ The compound was greenish-white and its solutions had a bluish fluorescence. 2-Acetamidofluoranthene (XXVII).- 2-Cyanofluoran thene (120 mg.) melting at 129-132° was partially dissolved 45 in alcohol (4.4 cc.). 6% Hydrogen peroxide (1.5 ec.) and 6 N sodium hydroxide (0.04 cc.) were added, and the solution was warmed to 60°. Oxygen was emitted, and the cyano- fluoranthene dissolved completely. After maintaining the solution at 60° for four hours, it was filtered, and cooled. 110 mg. of 2-acetamidofluoranthene precipi tated. The impure compound, upon recrystallization from alcohol, gave greenish-white needles melting at 245-247° (corr.). (8-Acetamidofluoranthene melts at 233°) (16). Calcd. for C17H110N: C, 83.27#i H, 4.49# Pound: C, 83.18# j H, 4.6l# Oxidation of 2-Bromofluoranthene.- 2-Bromofluoran thene (0,5 S«) melting at 112-114° was dissolved in glacial acetic acid (10 cc.). Chromic acid anhydride (1.4 g.) dissolved in water (1.3 cc.) and glacial acetic acid (0.4 cc.) were added. The reaction was kept at 50° for one hour, and then at 95° for three hours. Carbon dioxide was evolved copiously, and the solution became dark green. The flask was cooled, and yellow crystals of 3-bromo-9- fluorenone-1-earboxylie acid (XIX) were removed, washed thoroughly with dilute acetic acid and dried. Yield, 0.3 g»; m.p. 215-222°. After five recrystallizations from acetic acid and benzene and acetic acid, pale yellow needles, m.p. 235-236°, were obtained. Caled. for C^H OjBr: C, 5S‘47$j H, 2.29^ Found.: C, 55-4C$; H, 2.49$ By addition of water to the mother liquor, Q.Q5 g. of 9-fluorenone-1-carboxy11c acid (XVII), melting at 142-171°, was precipitated. This, after several recrystallizations from toluene, melted at 181-184°, and did not depress the melting point of authentic 9-fluorenone-1-carboxylie acid, ra.p. 188-189°, obtained by oxidation of fluoranthene in acetic acid according to the method of Fittig and Gebhard (2) . 9-Fluorenone (XVIII).- A small sample of 9- fluorenone-l-carboxyllc acid obtained by oxidation of 2-bromofluoranthene was melted, and an equal amount of cupric carbonate was added to the melt. The mixture was heated in a tube at 320° for 30 minutes. From the walls of the tube, yellow crystals of impure 9-fluorenone were obtained, m.p. 78-82°. (Reported 82°) (2). 3-Bromo-9-fluorenone (XX).- 3-Bromo-9-fluorenone- 1-earboxylic acid (0.1 g.), melting at 221-228°, was mixed with an equal amount of basic copper carbonate, and heated to 270° for 30 minutes. The copper carbonate decomposed, and yellow crystals of 3-bromo-9-fluorenone deposited on 47 the walls of the tube. The product was dissolved in ether, extracted four times with dilute sodium hydroxide to remove any sublimed starting material, and dried. Upon evaporation of the ether solution, yellow crystals were obtained, m.p. I58-I600. (Reported 1.61-162°) (47). A mixed melting point with authentic 3-bromo-9-fluorenone, prepared according to the directions of Miller and Bachmann (47) and melting at 159-160°, was not depressed. (Mixed m.p. 155-159°.) 2-(4-Broraobenzoyl)benzamide, prepared according to the directions of Miller and Bachmann (47)> melted after several recrystallizations from acetone and xylene at 212.5-213.5°• The melting point recorded in the literature is 184.5°-185°» bat both physical and chemical properties of the compound melting at 212.5-213.5° agree with those described in the literature (47). Calcd. for C ^ OgMBr: C, 55.28$; H, 3.31$ Pound: C, 55-52$; H, 3-71$ Hydrogenation of 3-Bromo-9-fluorenone.- 3-Bromo- 9-fluorenone (20 rag.), melting at 149-15^°* was dissolved in ether (20 ee.), platinum oxide (0.05 g.) was added, and the solution was subjected to 35 lbs. of hydrogen pressure for four hours. The ether was evaporated, and the residue 48 recrystallized from alcohol. The less soluble fraction probably contained 3*-b**omof luorene, and melted at 82-85°. Prom the mother liquor a white solid, 3-bromo-9-fluorenol (XXI), m.p. 140-144°, was obtained by addition of water. (Reported 142-145°) (55). SUMMARY 1. 2-Broxnof luoranthene has been synthesized by nitrating fluoranthene, reducing the 3~nitrofluoranthene formed to 3«aminofluoranthene, converting 3-aminofluoranthene to 3-acetylaminofluoranthene, brominating 3-&cetylamino- fluoranthene, hydrolyzing the 2-bromo-3-acetylamIno- fluoranthene formed upon bromination, and converting 2-bromo-3-e«ninafluoranthene sulfate into the diazonium salt, which was then reduced. 2. The structure of 2-bromofluoranthene has been proved by oxidative degradation to 3-bromofluorenone and 9»fluorenone-l-earboxylic acid. 3. 2-Cyanofluoranthene has been prepared from 2-bromo- fluoranthene by treatment of the latter with cuprous cyanide at high temperatures, and was hydrolyzed with hydrogen peroxide and sodium hydroxide to form 2-acetamidofluoranthene. 4. Both 3**ajninofluoranthene and 2-bromo-3-3uni.nofluoranthene have been shown to form dlacetyl derivatives. 5. The nitration of fluoranthene has been improved, and both 3-nitrofluoranthene and 8-nltrofluoranthene have been Isolated from the nitration mixture. 50 6. The following new compounds have been prepared: 8-nitrofluoranthene, 3-diacetylaminofluoranthene, 2-*bromo-3^acetylaminofluoranthene, 2~bromo-3-diaeetyl- aminofluoranthene, 2-bromo-3-aminofluoranthene sulfate, 2-bromofluoranthene, 2-cyanofluoranthene, 2-acetamido- fluoranthene, and 3-bromo-9-fluorenone-l-carboxylic acid. BIBLIO GR APH Y BIBLIOGRAPHY 1 . Goldschmiedt, Ber., 10, 2022 (1877). 2. Pittig and Gebhard, Ber., 10, 2141 (1877). 3. Pittig and Gebhard, Ann., 193, 142 (1878). 4. Fittig and Liepman, Ann., 200, 3 (1880). 5. Goldschmiedt, Ber., 11, 1581 (1878) (Claim of priority for "Idryl"). 6. Goldschmiedt, Monatshefte, I, 221 (1880). 7. Goldschmiedt and von Schmidt, Monatshefte, 2, 1 (1881). 8 . Graebe, Ber., 37, 4145 (1904). 9. Mayer, Ber., 46, 2579 (1913). 10. von Braun and Reutter, Ber., 59, 1922 (1926). 11. von Braun and Anton, Ber., 62, 145 (1929). 12. Kruber, Ber., 64, 84 (1931). 13* von Braun and Mamz, Ber., 63, 2608 (1930). • -t HI Tobler, Holbro. Sutter, and Kern, Helv. Chlm. Acta, 24E, 100 (1941). 15* von Braun and Manz, Ann., 488, 111 (1931). 16. von Braun and Manz, Ann., 496, 1J0 (1932). 17* Catsiff, Master's thesis, University of Southern California. 18. Bamberger and Hooker, Ann., 229, 102 (1885). 19* Campbell and Easton, J. Chem. Soe., 340 (1949). 20. Buu-Hoi and Cagniant, Rec. trav. chim., 62, 719 (1943). 21. Buu-Hoi and Cagniant, Ber., 77, 121 (1944). 52 22* Campbell and Easton, J. Chem. Soe*, 342 (1949). 23. Cook and Laurence, J. Chera. Soc., 1431 (1936). 24. Orchln and Reggel, J. Am. Chem. Soe., 69, 505 (1947). 25- Bergmann and Orchln, J. Am. Chem. Soc., 71, 1917 (1949). 26. Campbell and Gow, J. Chem. Soc., 1555 (1949). 27. Dilthey and Henkels, J. prakt. Chem., 149, 350 (1937). 28. Allen, Bell, Bell and Allan, J. Am. Chem. Soc., 62, 658 (1940). 29. Mertel, Master's thesis, University of Southern California (1948). 30. Campbell and Wang, J. Chem. Soc., 1513 (1949). 31. Tucker, J. Chem. Soc., 2182 (1949). 32. Forrest and Tucker, J. Chem. Soc., 1137 (1948). 33. Tucker and Whaliey, J. Chem. Soc*, 3213 (1949). 34. Tucker and Whaliey, J. Chem. Soc., 632 (1949). 35. Tucker and Whaliey, J. Chem. Soc., 50 (1949). 36. Bergdolt and Ballauf, U. S. Patent 1,990,018. 37. Kranzlein, Ber., 71B, 2328 (1938). 38. Meyer and Falta, Germ. Patent 734,882 (1943); Chem. Abstr., 38, 1252 (1944). 39. Liebermann and BoHert, Ber., 15* 226 (1882). 40. Abegg, Ber., 24, 949 (1895). 41. Quincke, Ber., 21, 1454 (I892). 42. Scholl and Stoll, Ber., 40, 1700 (1907). 43. Pschorr and Schroter, Ber., 35, 2728 (1902). 44. Ullmann and Conzettl, Ber., 53, 828 (1920). 53 45- Schaarschmldt, Ber., 4£, 2678 (1916). 46. Pisovschi, Ber., 41, 1434 (1908). 47. Miller and Bachmann, J. Am. Chem. Soc,, 54, 2444 (1935). 48. Huntress, Pflster and Pflster, J. Am. Chem. Soc., 64, 2845 (1942). 49. Courtot and Vignatl, Bull. soc. chlm., 41, 58 (1927). 50. Prance, Heilbron and Hey, J. Chem. Soc., 1364 (1938). 51. Newman, Org. Synth., 21, 89 (1941). 52. Noller, Org. Synth. Coll., Vol. 2, 568. 53. Ullmann and Eiser, Ber., 49, 2154 (1916). 54. DeMilt and Van2andt, J. Am. Chem. Soc., 58, 2044 (1938). 55. Miller and Bachmann, J. Am. Chem. Soc., 54, 2447 (1935).

Linked assets

University of Southern California Dissertations and Theses

Conceptually similar

PDF

Syntheses in the fluoranthene series

PDF

Syntheses in the thianaphthene series

PDF

Studies on alpha-naphthylglyoxylyl derivatives

PDF

Second-order nucleophilic substitution reactions of cyclobutane derivatives: A study of the stability of pentacoordinate carbon

PDF

The reaction of phenylmagnesium bromide with methyl B-benzoylpropionate and with diethyl succinate

$Preparation of different modifications of sodium soaps and their characterization by X-ray diffraction$

PDF

Preparation of different modifications of sodium soaps and their characterization by X-ray diffraction

PDF

Kinetics and mechanism of the substitution of water in aquapentacyanocobaltate (III) by pyridine

PDF

The chlorinolysis of carbon-sulfur bonds

PDF

The purification and study of inulin

PDF

The stereochemical course of the nucleophilic displacement of cyanide from alpha-ferrocenyl-alpha-aminonitriles, and model experiments for the synthesis of optically active alpha-ferrocenyl alkyl...

PDF

The acid catalyzed isomerization and dimerization of styrene oxide

PDF

I. Intramolecular reaction of alkenyl substituted silylenes. II. Determination of the relative migratory aptitudes of a trimethylsilyl group versus a hydrogen to a carbenoid center

PDF

The synthesis and testing of some alkyl substituted thyroxine analogs

PDF

Using van der Waals clusters to orient reactants: HBr-N2O, HBr-CO2, HCI-CO2

PDF

Some properties of the tetrakis (ethylenediamine)-u-dioldichromium (III,III) and - Dicobalt (III,III) complex ions

PDF

A study of the reactions of phosphorus pentachloride with trimethylamine

PDF

The reaction H+ClCN to CN+HCl

PDF

The rate of aquation of the sulfito ligands in disulfitotetracyanocobaltate (III) ion

PDF

Studies on the determination of thorium in the presence of rare earths

PDF

Kinetics of the reductive elimination reaction of trans-bromohydroxytetracyanoplatinate ion with thiosulfate and tetrathionate ions

Asset Metadata

Creator Menkes, John Hans (author)

Core Title Syntheses of fluoranthene derivatives with substituents in the 2-position

Contributor Digitized by ProQuest (provenance)

Degree Master of Science

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag chemistry, organic,OAI-PMH Harvest

Language English

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-791922

Unique identifier UC11348055

Identifier EP41588.pdf (filename),usctheses-c17-791922 (legacy record id)

Legacy Identifier EP41588.pdf

Dmrecord 791922

Document Type Thesis

Rights Menkes, John Hans

Type texts

Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection)

Access Conditions The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the au...

Repository Name University of Southern California Digital Library

Repository Location USC Digital Library, University of Southern California, University Park Campus, Los Angeles, California 90089, USA