REPORT NUMBER III

SYNTHESIS OF p-TRIFLUOROMETHYL-TOLUENE AND3 ,6-BIS( TRIFLUOROMETHYL)PHENAI'THRENE

SUSING SULFUR TETRAFLUORIDE

FINAL CCUREHENSIVE REPORT

Andrew J. Woytek, James F. Tompkins (Investigators)

David R. Latshaw, Barton Milligenand Ralph E. Mayo (Analytical Support)

,Kp"i± 19 (0

Supported by

U. S. ARMY MFDICtL RESFARCH !.ND DKV¢ELOPM*NT COMMA!%DWashinF, on, D, C. 20314

Countrac Fo. D;JA-7-7o--o7 ' -07',

Air P-oducts r.nd Chemicals, Inc.Allentown,. Pennsylvania 18105

&W-vp-u ..

REPORT NUMBER III

SYNTHESIS OF p-TRIFLUOROMETHYL-TOLUFNE AND3,6-BIS(TRIFLUOROMETHYL)PHENAi•TH!iENE

USING SULFUR TETRAFLUORIDE

FINAL COMPREHENSIVE REPORT

Andrew J. Woytek, James F. Tompkins (Investigators)

David R. Latshaw, Barton Milliganand Ralph E. Mayo (Analytical Support)

April 1970

Supported by

U S. ARMY MEDICAL RESEARCH AND DEVELOPMENT COMMANDWashtigton. D. C. ?0314

Contract No. DADA-17-70-C-0007

Air Products az.d Chemicals, Inc.Allentown, Pennsylvania 18105

I. Susmmry

The object of this work was to investigate, on a laboratory scale,the individual reactions of SF4 with p-toluic acid to producep-trifluoromethyl toluene and of 3,6-phenanthrene dicarboxylicacid to produce 3,6-bis(trifluoromethyl)phenantharene. This lab-oratory data was t, serve as a basis for scaleup of this reactionsto a conmercial process.

A total of 46 runs were conducted during this investigation with16 runs performed with p-toluic actd in a 300 ml autoclave, 10runs with p-toluic acid in a 170 ml autoclave, and 20 ains with3,6-phenanthrene dicarboxylic acid in the 300 ml autoclave. Theparameters investigated were temperature over the range of 206Cto 225eC, pressure over the range of 140 to 3,000 psig, reactiontimes from one to 18 hours, SF4 concentrations bt 50% to 4,500%excess, catalysis with hydrogen fluoride and the use of inertsolvents for the 3,6-phenanthrene dicarboxylic acid runs.

The p-toluic acid i.action was initially studied in a 300 mlhastelloy autoclave and a 78 % p-trif.luoromethyl toluene conversionwas obtained at reaction conditions of 1600 C, 1600 psig, 16 hourreaction time with a 50% molar excess of SF4. Recycle of the p-toluic acid fluoride generated during this reaction would increasethe yield of p-i;rifluoromethyl toluene to over 95% for these con-ditions. This reaction was scaled to a 1750 ml stainless steelautoiclave in which a total of ten runs were made. The conversionto p-trifluoromethyl toluene using similar reaction conditionsaveraged 72% (05T to 85% range) for these runs and the yield aver-aged 87% (77 to 100% range) including recycle of the p-toluic acidfluoride. Purification of the crude reactioiv product by distilla-tion gave a 90% recovery of >99% purity p-trifluoromethyl toluenefrom the reaction mixture. From this series of reactions, two 1500grams samples of p-trifluoromethyl toluene was, delivered to theWalter Reed Medical Center.

Twenty reactions of 3,6-phenanthrene dicarboxylic acid or its deri-vative 3,6-phenanthrene dicarbonyl fluoride were performed in the300 ml autoclave. Relatively pure (>95%) 3,6-phenanthrene dicar-bonyl fluoride was produced in quantitative yields from 3,6-phenan-threne dicarboxylic acid by reaction with SF4 at temperatures cf1I0 to 1600C. ,The highest conversion (22.5%) of 3,6-bis(trifluoro-methyl )phenanthrene was obtained by suspendi.ng the -,,6-phenanthren#.,dicarboxylic acid in lienzotrifluoride and reactiag at a temperature

2

of 210 to 2204C, pressure of 1950-2150 psig, reaction time of16 hours with a 1100% excess of SF4. In addition, a 17.5%yield of 3-trifluoromethyl phenanthrene-6-carbonyl fluorideand 2.4% yield of 3,6-phenanthrene dicarbonyl fluoride was ob-tained. A similar reaction performed at a lover temperaturegave a lower conversion (8.1%) to 3,6-bis(trifluoromethyl)phen-anthrene but a higher yield of the intermediates (48% 3-trifluoro-wethyl phenanthrene-6-carbonyl fluoride and 26% 3,6-phenanthrenedicarbonyl fluoride). This yield data is based on an analysisof the crude reaction mixture by quantitative GLC and TLC analysis.These analytical tools were developed during the course of thisstudy and can be now routinely used for analysis of 3,6-bis(tri-fluoromet~hyl)phenanthrene directly. The major intermediates(3-trifluoromethyl pheianthrene-6-carbonyl fluoride and 3,6-phenanthrene dicarbonyl fluoride) can be quantitatively deter-mined by reacting the crude reaction mixture with methanol anddetermining their concentrations based on the response of thecorresponding methyl esters. A purified sample of 3,6-bis(tri-fluoromethyl)phenanth;-cne was not obtained from these reactionsbut studies on the soxhlet extractors showed promise that sep-aration and isolation is possible.

A sample of purified 3,.6-bis(trifluoromethyl)phenanthrene wasobtained by decarboxylating the 3,6-bis(trifluoromethyl)phenan-threne-9-carboxylic acid. Identification of this compound (sectionV-A) was confirmed by IR, mekting point, NMR, UV and elementalanalysis. This sample served as a standard for GLC and TLC analysisof the crude reaction product.

Corrosion data gathered during the course of the p-toluic acidreactions showed a corrosion rate of <0.002 inches per year on316 staialess steel under reaction conditions.

An economic evaluation of the production of 3,6-bis(trifluoromethyl)phenanthrene based on a 20% 2onversion to 3,6-bis(trifluoromethyl)phenanthrene plus an additional 30% yield of recycleable inter-mediates showed that a selling price (excluding 3,6-phenanthrenedicarboxylic acid costs) of % $15/pound could be achieved at 30,000to 50,000 lbs per year 3,6-bis(trifluoromethyl)phenanthrane. Forsmaller requirements, (%,3,000 lbs/yr), the selling price (excluding3,6-phenanthrene dicarboxylic acid costs) would be 440/lb. Thesefigures reflect an expected SF4 aelling prize of $10 per pound atthe lover production rate and $3 per pound &t the higher productionrate.

3.. . .. , T

II. Foreword

This work was performed for the Walter Reed Army Institute ofResearch, Washington, 0. C. 20012 under Contract No. DADA-17-70-C-0007 as issued by the U.S. Army Medical Research and De-velopv-rTt. Command, Washington D.C. 20315. The program wasconduc-e" bc.'i.en July 1, 1969 and February ., 1970 by AirProducts and Chemicals, Inc. under the direction of J. F,Tompkins, (215-395-7261) principle investigator, at itsResearch and Development Department located at Trexlertown,Pennsylvani a.

The program consisted of studying the individual reactions ofSF4 with p-toluic acid and 3,6-phe-anthrene dicarboxylic acidto produce the corresponding trifluoromethyl function in placeof the carboxylic acid function. The p-toluic acid reactionswere performed in a 300 ml and 1750 ml autoclave while the phen-anthrene reactions were performed only on the 300 ml scale. Theoverall reactions under study are detailed below in I and II,with the major intermediate reactions indicated in Ia, Ib, II(a),IIb, IlIc.

I. CH3-- COOH + 2SF4 CH--- CF3 + 2SOF2 + HF

Ia. CH3 . COOH + SF4 4 CH3•• CF 3 + SOF 2 + HF

1b Ch. •- C0O + SF4 - CH 30 CF3 + SOF 2

4

II.+ 48F4 -.--- + 4SOF2+2HF

COOH COOH CF3 CF3

Ila. 4 2SF4 - Q + 2SOF2+2HF

COON COOH COp COF

IMb. + SF4 + SOF 2

CO COF CC CF3

HYIlc. + 2SF4 + 230F2

COF COF CF3 CF3

The basis of this study vas unpublished work previously performedby the Air Products and Chemical's Research and Development De-partment and open literature publications on the reactions ofSF4 -.

U5

TABLE OF CONTENTS

Page

I. SUMMARY. . . . . . . . . . . . . . . . .. . .. 2

II. FOREWORD . . . . . . . . . . . . . . . . . . . . . .* . . . 4

III, EXPERIMENTAL PROCEDURE . ................. 1 1

IV. DISCUSSION AND AESULTS ............. ..... ... . 13

A. p-TOLUIC ACID REACTIONS - 300 ML AUTOCLAVE . .*. . . . 13

B. p-TOLUIC ACID REACTIONS - 1750 ML AUTOCLA7 . .*. . . . 15

C. CORROSION DATA - p-TOLUIC ACID REACTIONS .. . 16

D. 3,6-PHENANTHRENE DICARBOXYLIC ACID REACTIONS -

300 ML AUTOCLAVE . . . . . . . . . . . . . .. ... 17

E. ECONOMIC EVALUATION - 3,6-PHENANTHRENE DICARBOXYLIC-ACID PROCESS . . . . . . . . . . .......... 21

V. SYNTHESIS AND IDENTIFICATION O0' PURE COMPOUNDS . .... 22

A. 3,6-BIS(TRIFLUOROMETHYL)PHENANTKRENE ............. 22

B. 3,6-PHENANTHRENE DICARBONYL FLUORIDE ............ .. 23

C. 3,6-BIS(CAR2OMETHOXY)PHWANTHRENE ..... ........... 24

D. 3-CARBOMETHOXY-6-¶RIFLU(AIOMET1YL PHENANTHRENE ...... 24

E. ELEMENTAL ANALYSIS - 3,6-PHENANTHRENEDICARBOXYLIC ACID. . . . ............. . 24

VI. ANALYTICAL PROCEDURE AND RESULTS - p-TRIFLUOROMETHYLTOLUENE .............................. 25

VII. ANALYTICAL PROCEDURE AND RESULTS - 3,6-BIS(TRIFLUORO-METHYL)PHENANTHRENE ................... ........ 26

A. INFRARED SPECTROSCOPY .................... 26

B. ULTRAVTOLFT SPECTROSCOPY ....................... 27

6

TABLE OF CONTENTS (Continued)

Page

C. GAS CHROMATOGRAPHY . . . . . . . . . . . . . . . . . . . . 28

D. NUCLEAR MAGNETIC RESONANCE SPECTRAL ANALYSIS ........ .. 31

E. MASS SPECTRAL ANALYSIS AND GAS CHROMATOGRAPH -

MASS SPECTRAL ANALYSIS .......... . ........ 32

F. THIN LAYER CHROMATOGRAPHIC ANALYSTS ......... . 33

G. SOLVENT EXTRACTION STUDIEU. ....... ................ 35

H. COLUMN CHROMATOGRAPH STUDIES ...... ............. .. 36

VIII. CONCLUSION AkD RECOMMENDATIONS ....... ................ 38

IX. DISTRIBUTION LIST .......... ........................ 94

X. DD FOFm 1473 (DOCUMNT CONTROL DATA - R&D) ........ . . 95

7

YI

LIST OF TABLES

Page

TABLE I - P-TOLUIC ACID REACTION CONDITIONS - 300 ML,AUTOCLAVE.. ....... .. o.. #.. .. .. .. .. . . 41

TABLE II - P-TOLUIC ACID REACTION CONDITIONS - 1750 MLAUTOCLAVE . . . . . . . . . . . . . . . . . . . . . . . 42

TABLE III - P-TRIFLUOROMETHYL TOLUENE SAMPLES DELIVERED TOCONTRACTORS. . . . . . . . . . . . . . . . . . . . . .

TABLE IV - 3,6-PHENANTHRENE DICARBOXYLIC ACID REACTIONCONDITIONS - 300 ML AUTOCLAVE . . . . . . . . . . . . . .

TABLE V - ELEMENTAL ANALYSIS OF 3,6-PHENANTHRENE DICARBOXYLICACID . . . . ..... .. . ....................... . # . . 45

TABLE VI - INFRARED OBSERVATIONS - 3,6-PHFNANTHRENE DICARBOXYLICACID REACTIONS ......... . . . . . . . . .o :6

TABLE VII - GAS CHROMATOGRAPHIC ANALYSIS - 3,6-PHENANTHRENEDICARROXYLIC ACID REACTICNS ... . . . 4.7

TABLE VIII - SOLIDS PRCBE MASS SPECTRAL DATA - RUN #26 . . . . . . 48

TABLE I' - GAS CHROMATOGRAPHIC - MASS SPEC`TRAL ANALYSIS - RUN #26.. 49

TABLE X -- THIN LAYER CHROMATOGRAPHY ANALYSIS QUANTITATIVERESULTS ......... . . . . .......................... 50

TABLE XI - THIN LAYER CmIOMATOGRAPHY ANALYSIS QUALITATIrEOBSERVATIONS ..... ......... ... ............. .. i5

TABLE XII - COLUMN' CHROMATOGRAPHY RESULTS - RUN #21. . . . . . .... 52

8

LIST OF FIGURES

Pape

FIGURE I - REACTOR FLOWSHEET - 300 CC. REACTOR. . . . . . . . . . . . . 53

F'IGURE II - P-TRIFLUOROMETHYL TOLUENE YIELD VS. REACTION TIK{ . . . . .54

FIGURE III - SFh SYNTHESIS WITH P-TOLUIC ACID - T (P ATURE VS.PRESSURE . . . . . . . . .0. . . . . . .. 0. .. 0. . .. 55

FIGURE IV - IR SPECTRUM - P-TRIFLUOROMETHYL TOLUENE .. ... . . . . . 56

FIGURE V - GAS CHROMATOGRAM - P-TRIFLUOROMETHYL TOLUENE . . . . . . . 57

FIGURE VI - IR SPECTRUM - 3,6-BIS(TRIFLUOROKME L)P•IrNANTHREIý. ..... 58

FIGURE VII - ,y SPECTRUM - 3,6-BIS(TRIFLUOROMETHYL)PHKNANJTh-lEE . . .. 59

FIGURE VIII - IR SPECTRUM - 3,6-PHENANTHRENE DICARBONYL CHLORIDE . .. . 60

FIGURE IX - IR SPECTRUM - 3,6-PHENANTHRENE DICARBONYL FLUORIDE .... 6!

FIGURE X - IR SPECTRUM - 3,6-PHENAiTHRENE DICARBOXYLIC ACID ....... 62

FIGURE XI IR SPECTRUM - 3,6-BIS(TRIFLUOROMETIiYL)PHENANTHRENE-9-CARBOXYLIC ACID . . . . . . ..................... . 63

FIGURE ":II - IR SPECTRUM PHENA*THRM . . . .... .............. o 6os

FIGURE XIII - IR SPECTRUM PHENEATHRENEQUJNONE . . . ..... ............ 65

FIGURE XIV - IR SPECTRUM - RUN #30o ......................... 66

FIGURE XV & X';I - Uli SPECTRUM - 3,6-BIS(TRIFL-UOROMETHYL)PHENANTHRENE. . 67 & 68

FIGURE XVII - UV SPECTRUM - 3,6-BIS(TRIFLUOROMETHYL)PHENAKNTREN-9-CARBOXYLIC ACID ..................... 69

FIGURE XVIII - UV SPECTRUM - RUN #23 .......... . ................. T0

FIGURE XII - UV SPECTRUM - SAMPLE 5022-19B - FRACTION COLLECTED FROMCOLUMN CHROMATOGRAPHY OF RUN #21 . ............ . . . 71

FIGURE XX - rAS CHROMATOGRAM - RLIN NO. 41 .......... ............... 72

FIGURE XXI - GAS CHROMATOGRAM - 3,6-BIS(TRIFLU7IOMETHYL)PHENANTrENEWITH INTERNAL STANDARD (P-TRIFLUOROMbTrYL TOLUENE) . . . . 73

9

LIST OF FIGURIES (Continued)

Page

FIGURE XXII - GAS CHROMATOGRAM - SAMPLE 26-4 . . . . . . . . . 74

FIGURE XXIII - NMR SPECTRUM - 3,6-PHENANTHRENE DICARBOXYLIC ACID. . . . 75

FIGURE XXIV - NMR SPECTRUM - 3,6-PHENANTHRENE DICARBONYL FLUORIDE . . . 76

FIGURE XXr - NMR SPECTRUM - RUN #21 . . . . . . . . . . . . . . . . .

F ItURE XXVI - NMR SPECTRUM -RUN #3.... ..... . . . . .8

FIGURE XXVII - MASS SPECTRAL CHROMATOGRAM - RUN #26 . . . . . . . . . . 79

FIGURE XVIII - GAS CHROMATOGRAM - RUN #26. . . . . . . . . . .80

FIGURE XXIX - 7-AS CHROMATOGRAM - RUN #30 ................ 81

FIGURE XXX - GAS CHROMATOGFPA - METHOXYLATED - RUN #3C . .. . . . . . . 82

FIGURE XXXI - THIN LAYER CHROMATOGRAPHY PLATE - 3,6-BIS(TRIFLUORO-METHYL PIENANTHRENE AND CR!UDE REACTION PRODUCTS . .*. .. 83

FIGURE XXXII & XCOCI!I - THIN LAYER CHROMATOGRAPHY PLATE - 3,6-BIS(TRIFLUOROMETHYL)PHENANTHRENE, 3,6-I s ( CARmO-METHOXY)PHENANTHRENE AND METHOXYLATEDREACTION PRODUCTS ....... ............... 8 & 85

FIGURE XXXIV - EX7"-ACTION STUDIES - RUN #23 . .................. 86

FIGURE XXXV - EXrRACTION STUDIES - iUN #25. . . . . . . . . . .... . 87

FIGURE XXMVI - EXTRACTION STUDIES .. RUN #26 ...... ............ 88

FIGURE XXXVII - EXTRACTION STUDIES - RUN C27 ...... .............. 89

FIGURE XXXVIII - EXTRACTION STUDIES - RUN #30 . . ...... ............ 90

FIGURE XXXIX - EXTRACTION STUDIES - RUN #31 ..... .............. ... 91

FIGURE XXXX - COLU71N CHROMATOGRAM OF ACETONE EXTRACT - RUN Y•21 ....... 92

FIGURE XXXXI - PROPOSED PRODUCTION PROCESS - SF4 REACTION WITH3,6-PHFNANTHRENE DICARBOXYLIC ACID ...... ........... 93

10

i . . . . . . .

III. Experimental Procedure

Figure 1 is a flow diagram of the 300 ml autoclave used in theseexperiments. For the p-trifluoromethyl toluene runs made in the1750 ml autoclave, the equilment and experimental procedure isthe same except that the 300 ml hastelloy rocking autoclave isreplaced by a 1750 ml stirred stainless steel autoclave. Thefollowing basic proceiure was followed for both the p-toluicacid and 3,5-phenanthrene dicarboxylic acid runs with variationsin time and temperatures for the different runs.

1. The 300 ml hastelloy pressure vessel is purged withN2 and then pressure tested to 2,000 psig @ roomtemperature.

2. The reactor is vented, evacuated to 1 mm Hg and ventedto the .i nosphere.

3. A charge of dry acid is imnLediate'y added to the vessel.For the p-toluic acid runs this was normally 57 grams(0.42 moles) of aiid while for the 3,6-phenanthrenedicarboxylic acli, runs this was normally 10 grams(0.037 moles).

4. The vessel is again evacuated to 1 mm Hg and is cooledto -40OF in a dry ice - acetone ba~h.

5. A weighed amount of gaseous SF4 is condensed in thereaction vessel. For the p-toluic acid runs this wasnormally 157 grams (1.43 moles), while for the 3,6-phenanthrene dicarboxylic acid runs SF4 charges from24 to 356 grams (0.2 to 3.3 moles) were used.

6. The reactor is allo;!d to warm to room temperaturewith the pressure increasing to approximately 140 psig.

7. The reactor is placed in the heating furnace and heatedto the desired temperature over a one to two hour periodand allowed to react at this temperature for the pre-determined time (usually 16-20 hours).

8. At the end of the reaction time, the reactor is cooledto room temperature and vented to a caustic solution.

11

9. The reactor is opened after the pressure reaches atmos-pheric and the contents are poured into a polyethylenebottle. In the case of the 1750 ml reactor, the ma-terial is removed through a dip tube.

10. The crude reaction mixture is then analyzed. For thep-toluic acid runs, the analysis is performed on thegas chromatograph to determine p-toluic acid, p-toluicacid fluoride, p-trifluoromethyl toluene content andthe material is processed as indicated below. For the3,6-phenanthrene dicarboxylic acid runs, the gas chroma-tograph is used to determine the 3,6-bis(trifluoromethyl)phenanthrene content and the material is further workedup through extractions, TLC analysis, and mass saectro-graph analysis detailed in subsequent sections of thereport.

The following procedure was used to work up the reaction mixturefror the p-toluic acid runs to purified p-trifluoromethyl toluene.

1. The crude mixture from up to three separate reactionsis mixed with enough powdered NaF to react with thetheoretical amount of HF generated during the reactions.

2. This mixture is allowed to react for approximately onehour aid is then filtered to remove the NaF.HF.

3. The solution is distilled at atmospheric pressure in aone inch diameter, 2 feet long glass distillation columnpacked with stainless steel "Canon" packing (size 0.16 x0.16). A one to one reflux ratio was used and the p-tri-fluoromethyl toluene cut was taken between 130 and 1320 C.

4. The 0o-trifluoromethyl toluene cut is analyzed on the gaschromatograph to determine purity.

12

IV. Discussion and Results

A. P-Toluic Acid Reactions - 300 ml Autoclave

A series of fifteen reactions were performed in the 300 mlautoclave to study the parameters which affect the conversionof p-toluic acid and SF4 to p-trifluoromethyl toluene. Thepurpose of these runs were to determine the conditions whichoptimize the yield of p-trifluoromethyl toluene and to obtaindata which would permit scale up of this reaction and thesubsequent reactions of 3,6-phenanthrene dicarboxylic acidwith SF 4 . The operating data and results for these runs arepresented in Table I.

Runs 1 through 5 were used to obtain analytical samples andto determine a suitable workup technique to purified product.No quantitative yield data was obtained on these runs exceptthat through workup of Run No. 5 it was found that the yieldof p-trifluoromethyl toluene was very low since over 50% ofthe acid charged to the reactor was recovered. This was doneby reacting the crude with a 10% NaOH solution and acidifyingthe solution to recover the acid. This SF 4 reaction was per-formed at 120°C for 20 ix.-ýrs and indicated that the reactiondoes not proceed to the trifluoromethyl group In significantyield at this temperature.

Runs #6 and #9 were essentially duplicate runs performed atnominal conditions of 150°C,lI00 psig and a reaction periodof 8 hours. Yields of p-trifluoromethyl toluene were 38%and 33% for these two runs. Run #C0 was performed at essent-ially the same temperature and pressure with the reactiontime increased to 18 hours. In this case the yield was im-proved to 53%. For Run #11, the reaction time was restoredto eight hours and the temperature increased to 1900 C with &

corresponding increase in pressure to 1350 psig. The yieldof p-trifluoromethyl toluene was 49% for this run. Run #14was performed using the elevated temperature and pressure of#11 and the prolonged time period of #10. In this case theyield of p-trifluoromethyl toluene was incroased to 68%. tiun#15 was made to evaluate the effect of pressure on the ceaction.The charge of p-toluic acid was increased by 50% and the samewolar ratio of SF4 was used. This resulted in a larger chargeto the reactor and a corresponding increase in total pressure.For this run, the reaction temperature was 1600C, the reactionpressure was 2000 psig, and the reaction time was 18 hour.. The

13

yield of p-trifluoromethyl toluene was 78% for this run.This represento the highest yield of any of the runs andestablished the conditions under which yields of 75-80%could be achieved.

Figure II is a plot of the yield data discussed above atconstant pressure, temperature and reactant concentrations.In general, increasing the reaction time, temperature, andpressure all tended to increase the yield with the increasedpressure being particularly significant. Contrasting Run#15 to Run #11, the yield of p-trifluoromethyl toluene wasincreased from 53% to 78; by increasing the pressure from1100 psig to 2000 psig while keeping the temperature con-stant at 1500C and the reaction time at 18 hours. Also,plotted on Figure II is the yield of p-trifluoromethyltoluene plus p-toluic acid fluoride at the various reactionconditions. This yield represents the yield which could beexpected if che acid fluoride is recycled as would be doneon a commercial scale. For Run #15, this yield was 97.4%.In none of the runs was any attempt made to recycle the acidfluoride. In general, this yield dropped with increasingtemperature and longer reaction times. Therefore, it isexpected that increasing the reaction time (>18 hours) andgoing to higher temperature (>1900C) would not improve yieldsbut rather increase the amount of undesired products.

In addition to the runs already discussed, four other runswere performed. Runs #7 and #8 produced black solids (theappearance of coal) and no desired products. These runswere performed with a new supply of SF4 which was subsequentlyfound to contain >10% S2 F2 . All previous runs used materialcontaining less than 2% S2 F2 and gave a liquid product. Useof this material was discontinued and all subsequent runsused SF4 containing less than 2% S2 F2 .

Two runs were made using the p-toluic acid fluoride as thestarting material. This material was prepared by convertingthe acid to the acid chloride and reacting the acid chloridewith HF to obtain the acid fluoride. Run #12 was conductedusing the acid fluoride prepared in this manner with a 50%excess SFj4 at 1500C for 18 hours. This reaction failed top• •duce any n-tr fluoromethyl toluene and the acid fluoridewas recovered intact. This material was recharged to the

reactor along with an equal molar quantity of HF and q 50%excess of SF 4 . In this case a high yield (76%) of p-tri-fluorcmeth?,l toluene was obtained indicating the need forHF to catElyze the reaction. For reactions usinR the acidas the charge, HF is -renerated on an equal moeir blaris inthe conversion of the acid to the acid fluoride as the in-itial step of the reaction.

Attached in Figure III is the pressure-terrerature relation-ship for Puns No. 13 and 15. Run No. 13 was an acid fluoriderun while Run No. 15 was an acid r~an. The relative quantitiesof HF, SF4 and organic material w: re the same for both runsbut the resultant gasenus products are sliphtly different sincemore SOF 2 is generated in the acid run.

Workup of the crude material was performed by distillation in amanner similar to that ihlicated in the procedure section ofthe report. However, in these workups the crude react'.ori pro-duct was initially diluted with an equal volume of rentane andthe distillation was performed using a shorter column with noreelux. The workup was performed in two separate batches withRHi #9 and #10 constituting the initial batch and Runs #6, 11,14 and 15 constituting the second batch. Overall a total of86.5% of the p-trifluoromethyl toluene and 94.5% of the p-toluicacid fluoride were recovered based on the analysis of the crude.The total recovery of p-trifluorometayl toluene as nure material(>99%) was 76.5% of the analytical results, with the remainingmaterial contained in the high boilinp cuts.

A total of 161.3 grams of >99% purity p-trifluoromethyl toluenewas recovered from these runs. One hundred thirty crams ofthis material was shipped to Starks Associates Inc., 1280 Nia-gara Street, Buffalo, New York on August 27, 19i9,Q. The analyti-cal data for this samnle is contained in section VI nf thereport. The remaining material was retaicel bhy fic >'roductsand Chemictls, Inc., for analytical samnies qýni %i.ýre refer-ences.

B. P-Toluic Acid Reactions - 1750 ml AutocilFive

Ten runs were made in the 150r ml stairlv:2•. n,•- rijhclave toproduce a total of 3297 grams of p-trifluor(metriy ' y Iu,'ne.The operating conditions and resuitr 0l" t-,:,- ru contained

in Table TI.

15

The molar yield of p-trifluoromethyl toluene (based on GLCanalysis) averaged 72% for all ten runs and ranged from 57to 85%. The molar yield of p-trifluoromethyl toluene andp-toluic acid fluoride (based on GLC analysis) averaged 87%for all runs and ranged from 77 to 100%. The recove:y of'99% purity p-trifluoromethyl toluene through workup anddistillation was 90-91% of the analytical data. The averagemolar yield of recovered p-trifluoromethyl toluene (>9>%purity) based on the starting p-toluic acid was 62% - 65%based on data obtained f:,r the combination of Runs 32, 33,and 34 and Runs 38, 39. and 40. This data is detailed inTable II. No attempt was made during these runs to re-cover p-toluic acid fluoride and, therefore, no recoveredyield of p-trifluoromethyl toluene plus p-toluic acidfluoride was obtained.

Table III is a summary of the samples of p-trifluoromethyltoluene which were produced and delivered under this con-tract.

C. Corrosion Data - P-Toluic Acid Reactions

The hastelloy reaction vessel showed no visible corrosionduring this series of reactions but no quantitative data wasobtained on corrosion rate. A corrosion rate of 0.002 inches/yebr on 316 stainless steel was determined during the series

of reactions in the 1750 ml stainless steel reactor. Thisdata was obtained by measuring the weight loss of the re-actor's stainless stee?. (type 316) turbine agitator for thelast eight reaction runs in the reactor. The rate was cal-cuW.ated by assuming corrosion occurred only at the el,.-vatedtemperatures of the reaction, which amounted to a total of135 hours for these tests. Therefore, the calculated datawould represent a maximum corrosion rate since it ignores thetime in which the solution was in contact with the agitatorat lower temperatures. This data represents an average cor-rosion rate and does not consider any pitting or stress cor-rosion. However, the data does indicate that 316 stainlesssteel is a suitable material of construction for use in run-ning this type cf reaction.

16

D. 3,6-Phenanthrene Dicarboxylic Acid - 300 ml Autoclave

A total of twenty individual reactions of SF4 with 3,6-phenanthrene dicarboxylic acid or its derivative 3,6-phenanthrene dicarbonyl fluoride were performed in the300 ml hastelloy autoclave. In three of these runs (19, 27and 36), 3,6-phenanthrene dicarbonyl fluoride prepared in aprevious run was used while two other runs (42 and 45) useda mixture oZ 3,6-phenanthrene dicarboxylic acid and 3,6-phenanthrene dicarbonyl fluoride. The operating conditionsand results of these runs are summarized in Table IV. Asummary of the IR observation for *hese runs are given inTable VI and the GLC quantitative PE,'alysis for the runs aresummarized in Table VII.

The parameters studied in these reactions were temperatureover the range 20 to 2250 C, pressure over the range of 110to 2400 psi, SF4 ratio of 50 to 4500% excess, reaction timesof 1 to 18 hours and the effect of HF as a catalyst and theuse of inert type solvents. Because of the limited avail-ability of 3,6-phenanthrene dicarboxylic acid, the charge of3,6-phenanthrene dicarboxylic acid was generally limited to10 grams per run and in most cases large excesses of SF 4 wereused to obtain the desired pressure. In several. runs whereSF4 was used in only a moderate excess, the higher pressureswere obtained by adding N2 to the reactor.

The initial run of this series (#17) produced relatively pure(>95%) 3,6-phenanthrene dicarbonyl fluoride in a quantitativeyield. This reacticn was run at 1120 C using a large excessof SF4 to produce an autogeneou: pressure of 2400 psig. Thepurity was estimated based on a comparison to the IP spectrum(Figure IX) of a sample of 3,6-phenanthrene dicarbonyl fluoridesyn10lesized as indicated in Section V of the report. Run #18was performed in a similar manner at a temperature of 164 0C andagain produced primarily 3,6-phenanthrene dicarbonyl fluorideand no significant amount of 3,6-bis(trifluoromethyl)phenanthrene.Run #28 was subsequently performed at the same conditions as#17 to produce 3,6-phenanthrene dicarbonyl fluoride for use inother reactions.

Runs #19, 20 and 21 were made using anhydrous hydropen fluorideas a catalyst in an attempt to promote conversion to 3,6-bis(tri-fluoromethyl)phenanthrene. Exhaustiv,_- analysis of this materialby extraction, mass topectrgraph and TLC indicated substitutior.at the 9 and 10 position and a multitude of com.-ounds, including

17

some coifoluo,)O- in which the phenanthrene ring had been split.This dota was obtained by a combinaticn of column chromato-graphy and UV analysis as presented in Section VII-H andTable XII and NMR analysis as presented in Section VII-D andFigure XXV. GLC analysis of #21 (Table VII) showed 1% 3,6-bis(trifluoromethyl)phenanthrene with a number of otherunidentified compounds totaling %7% of the sample. Additionalwork was done with HF as a catalyst and using 3,6-phenanthrenedicarbonyl fluoride as the etarting material. These experi-ments were conducted in Runs #27 and #36 at temperatures ofapproximately 1000 C. In both cases, GLC analysis (Table VII)indicated less than 0.1% 3,6-bis(trifluoromethyl)phenanthreneand a variety of other compounds. Soxhlet extraction (Figure27) of #27 using heptane showed that only 24% of the materialcould be cxtracted. Run #31 was performed with 3,6-phenan-threne dicarboxylic acid as the starting material (in methylenechloride solvent) and using HF as a catalyst at a low tempera-ture (20 c) and produced >95% 3,6-phenanthrene dicarbonylfluoride and 0.1% 3,6-bis (trifluoromethyl)phenanthrene.

Since the above data indicated that HF had a determental effecton the reaction at elevated temperatures, its use was discon-tinued and further work was done without HF at temperatureabove 1800 C in an attempt to promote conversion to 3,6-bis(tri-fluoromethyl)pnenanthrene. Four runs (#21, 23, 25 and 26) weremade over the temperature range of 180 to 2200 C. By GLC analysisthese runs showed an improvement in the conversion to 3,6-bis(trifluoromethyl)phenanthrene, with run #26 containing 4.1% ofthe desired product. Run #26 was performed at 2200 C, 2500 psigand with a large excess of SF4. Mass spectral analysis (TableVIII) of #26 showed the presence of significant quantities ofcompounds corresponding to the molecular weights of 3,6-bis(trifluoromethyl)phenanthrene and 3-trifluoromethyl phenanthrene-6.-carbonyl fluoride and 3,6-phenanthrene dicarbonyl fluoride.

Based on these results which showed thAt a limited conversion to3,6-bis(trifluoromethyl)phenanthrene could be obtained at ele-vated temperatures, a run was mode at a high temperature whileusing an inert solvent to suspend the material during the re-action. Fun #30 was made at 185*C and 1900 psig using benzo-trifluoride as a solvent. GLC analysis (Table VII) of thismaterial shoved 8.2% 3,6-bis(trifluoromethyl)phenanthrene inthe crude product. Quantitative analysis (TAble X and Figure

18

XXXII) of this run by TLC gave 7.5% 3,6-bis(trifluoromethyl)phenanthrene, 26% 3,6-phenanthrene dicarbonyl fluoride, and48% 3-trifluoromethyl phenanthrene-6-carbonyl fluoride, whichamounts to a yield of 80% for product material or intermediates.This analysis was performed on the methoxylated reaction productas indicated in Section VII-F. NMR data (Figure XXVI) con-firmed the presence of the three major components in the sampleand an improved GLC analysis (Sectio:n VII-E and Figure XXX) onthe methoxylated product further confirmed the results obtainedby TLC.

Run No. 35 was made using a more dilute concentration of 3,6-phenanthrene dicarboxylir acid to benzotrifiuoride (20 gins. to100 gns.) with a corresponding reduction in SF4 concentrationsto a three fold excess. In this case, GLC analysis (Table VII)showed 2.5% 3,6-bis(trifluoromethyl)phenanthrene and only atrace of 3,6-phenanthrene dicarbonyl fluoride and 3-trifluoro-methyl phenanthrene-6-carbonyl fluoride by TLC analysis.

Run No. 37 was then performed as in exact duplicate to #30 withthe exception that it was necessary to use a new batch of (AGC-W71.4) of 3,6-phenanthrene dicarboxylic acid since all the previousbatch (AGC-W 71.3) had been consumed. In this case, GLC analysis(Table VII) showed 5.5% 3, 6 -bis(trifluoromethyl)phenanthrene andquantitative TLC analysis (Table X) showed a yield of 4.6% 3,6-bis (trifluoromethyl)phenanthrene, 27% 3-trifluoromethyl phenan-threne-6-carbonyl fluoride and 26% 3,6-phenanthrene dicarbonylfluoride. This amounts to a total yield of 57.6% for products andintermediates as opposed to the 80% figure obtained in #30.

Run No. 41 used the same concentration or 3,6-phenanthrene dicar-boxylic acid, benzotrifluoride and SF4 as #30 and was performedat a higher reaction timperature (210 to 220 0 C). This run pro-duced the highest yield of 3,6-bis(trifluoromethyi)phenanthreneof any of the runs. GLC analysis (Table VII) showed 17.5%3, 6 -bis(trifluoromethyl)phenanthrene in the crude solid cor-responding to a 19.0% yield. TLC analysis (Table X) showed 6.7%3, 6-biu(trifluoromethyl)phenanthrene in the crude reaction mixture(containing benzotrifluoride) which corresponded to a 22.4% yield.TLC analysis also showed a 2.4% yield of 3,6-phenanthrene di-carbonyl fluoride and 17.5% yield of 3-trifluoromethyl phenan-threne-6-carbonyl fluoride, gi,-*,ng a total yield or 42% for

19

product and intermediates. This run rroved to be the mostsuccessful in terms of product conversion while #30 was themost successful in terms of yield of product plus inver-mediates.

Runs #42 and 43 were made using a mixture of 3,6-phenmnthrenedicarboxylic acid and ?,6-phenanthrene dicarbonyl fluoride inthe benzotrifluoride solvent. These runs vere performed toevaluate conditions in which HF was present in less than themolar quantities present in a reactor starting with pare 3,6-phenanthrene dicarboxylic acid. Run #42 contains a ratio of6.1 parts 3,6-phenanthrene dicarbonyl fluoride to 3.6 parts3,6-phenanthrene dicarboxylic acid and was reacted at 1800 C.GLC analysis showed a 5.5% yield of 3,6-bis(trifluoromethyl)phenanthrene. TLC data on 3-trifluoromethyl phenanthrene-6-carbonyl fluoride and 3,6-phenanthrene dicarbonyl fluoridewere not obtained at this point. This reaction product wasreturned to the -reaction with an additional 20% of acid a""reacted at a higher temperature (220 0 C). In this case, GLCshowed <1% product and TLC analysis (Table X) showed verylittle of 3,6-bis (trifluoromethyl )phenanthrene, 3-trifluoro-methyl phenanthrene-6-carbonyl fluoride and 3,6-phenanthrenedicarbonyl fluoride and an unidentified compound running be-yond 3,6-bis(trifll -omethyl)phenanthrene on the TLC plate.

Run No. 46 was made using the temperature conditions of #40with an increase in the amount of benzotrifluoride. The benzo-trifluoride concentration was increased to bring its liquidconcentration to a comparable state to that used in #30; thatis, to compensate for the amount of vaporization between 180and 2200 C. This reaction was not successful in producing3,6-bis(trifluoromethyl)phenanthrene (c1% as indicated by GLCand TLC analysis. However, TLC analysis (Table X) did showa 33% yield of 3,6-phenanthrene dicarbunyl fluoride and 8%yield of 3-trifluorome.thyl phenanthrene-6-carbonyl fluoridewith the remaining materala staying at the origin.

A limited amount of work was done on attempting to isolatepure compounds from the crude reaction mixture. The mostpromising technique for concentrating the 3,6-bis(trifluoro-methyl)phenanthrene was obtained in the soxhlet extractionwith heptane as reported in Section VII-G. These studiesshowed that a 5 to 14 fold increase in 3,6-bis(trifluoro-methyl)phenanthrene concentration could be obtained. Fcrcrude reaction mixturre #26, the 3,6-bia(trifluoromethyl)phenanthrene was conct'ntrated from 4.1% to 19.1% by overniteextraction with heptane (Figure XXIII). This was the highestconcentration of 3,6-bia (tri fluoromethyl )phenanthrene obtainea

20

in any- of the fractions obtained by the soxhlet extraction.Since major emphasis in the program was to determine the op-timum reaction conditions and use analytical tools to analyzethe results, the work in this ar-a was limited. No attemptswere made to concentrate the reaction product from Run No. 41which originally showed 17.5% product in the crude reactionmixture.

E. Economic Evaluation - 3,6-Phenanthrene Dicarboxylic Acid Process

An economic evaluation of the production of 3,6-bis(trifluoromethyl)phenanthrene on a semi-commercial scale was made basedon the information gathered in this study. Figure XXXXI isa flowsheet of a production process based on a 3,6-phenanthrenedicarboxylic acid conversion of 20% to 3,6-bis(trifluorcmethyl)phenanthrene, 20% to 3-trifluoromethyl phenanthrene-6-carbonylfluoride and 10% to 3,6-phenanthrene dicarbonyl fluoride withan 80% recycle recovery of the intermediate products. SinceSF4 requirement per pound of 3,6-bis(trifluoromethyl)phenan-threne are large (3.5 lb. SF4/lb 3,6-bis(trlfluoromethyl)phenan-threne), the cost of SF4 is the most significant cost item inthe process. At 3, 6 -bis(trifluoromethyl)phenanthrene pro-duction rates of 3,000 lbs/yr, SF4 requirements would amountto approximately 10,000 lbs/yr at which SF4 is expected to bepriced in the $5-$l0/lb. range. At the higher cost, thiswould emount to an SF4 cost of t35 per pound of 3,6-bis(tri-fluoromethyl)phenanthrene. In addition, the cost of labor,depreciation, and return on investment would amount to ap-proximately $5/lb. The selling 'orice at 3,000 lb/yr 3,6-bis(trifluorometh•i.)phenanthrene wo!,ld then be estimated at $40/lbplus 1.9 times the per pound cost of the 3,6-phenanthrenedicarboxylic acid.

At higher production level of 30,000 to 50,000 #/yr 3,6-bis(trifluoromethyl)rhenanthrene, where SF4 requirements wouldexcess 100,000 #1 yr, the cost of SF4 is expected to be in therange of $3/lb. At this SF4 cost, the selling price would beexpected to be in the vicinity of $15!lb plus the additionalper pound cost of the 3,6-Tphenanthrene dicairooyvlic acid.

21

V. Synthesis and Idientification of Pure Compounds

A. .26Bis (trifluoronethyl)phenanthrene (b-TFMPý

To 0.1 g of copper sulfate in 16 ml of quinoline was added0.5 g of 3,6-bis(trifluoromethyl)phenanthrene - 9 - car-boxylic acid. The mixture was heated at 2150 C for 3 hours.After the mixture was cooled, 120 ml of benzene was added.The solution was filteb'ed, and the filtrate was washedthoroughly with 1N hydrochloric acid, IN potassium carbonate,water and then dried over calcium chloride. Filtering offthe calcium chloride and evaporation of the benzene producedtan colored crystals. Recrs.allization of these crystalsfrom absolute ethanol yielded 0.1189 g of slightly grey,needle-like crystals with m.p. 140.5 - 141.50C.

Anal. Calcd. for C, 6 H8 F6 : C, 61.16; H, 2.57; F, 36.27

Found: C, 60.99; H, 2.63; F, 36.12

NMR: All ring protons a-'e in place except for thosein the 3 and 6 positions.

Mass Spect: Calc. Molecular Weight, 314.23

Found, 314

Infrared: 'The strong absorbance at 7.55P" and 8.95/'indicates the presence of tvifluoromethylgroups. No absorbance at 5.5P to 6.0/'indicates the absence of a carboxylic acidgroup. (Figure VI)

Ultraviolet: Comparison of the extinction coefficient(k) below with those of phenanthreneand 3,6 - bis(triflucroriethyl)phenan-threne - 9 - carboxyli- acid indicatesthe phenanthrene ring is intact. (FigureVII)

X252 X301 X334

Phenanthrene k=50,000 k=13,000 k-250

3,6-Bis(tri-fluoromethyl)phenanthrene k-64,200 k-12,600 k=291

3,6-Bis (tri-

fluoromethyl)phenanthrene-9-c arbo•7li cacid k=52,200 k=11,000 k=435

22

Gas Chromatography: Dissolving a sample of 3,6-bis (trifluoromethyl )phenan-threne in acetone and then chro-matographing the sample showed(other than the solvent peak)one major product peak at 11.9minutes.

Directions for this type of decarboxylation were found in thefollowing references:

1. Rapoport, H., Williams, A. R., and Cisney, M. E.,J. Am. Chem. Soc., 73, 1418 (1951).

2. Nodiff, E. A., private communication from Bing T.Poon to James F. Tompkins, dated 11/4/69.

B. 3,6-Phenanthrene Dicarbonyl Fluoride (PDCF)

A 2:1 ratio of benzoic acid to 3,6-phenanthrene dicarboxylicacid was heated to 1350C. Thionyl chloride was added slowlyuntil it was in excess. After cooling and setting for 24 hoursthe excess thionyl chloride was distilled. The remz.ning solidswere washed with ether to remove the benzoyl chloride. Recry-stallation of the remaining material from a tetrahydrofuran ben-zene mixture gave white, needle-like crystals melting from 178-1810 C. This material was identified as being 3,6-phenanthrenedicarbonyl chloride. An infrared spectrum of this material isshown in Figure VIII.

The 3,6-phenanthrene dicarbony! chloride was then stirred for 16hours with excess hydrogen fluoride. Distillation of the excesshydrogen fluoride, and recrystallation of the solids from a tetra-hydrofuran-benzene mixture gave white, needle-like crystals meltingfrcm 234-2360 C.

Anal. Calcd. for C1 6 H8 02 F2 : C, 71.11; H, 2.98.

Found: C, 71.0; H, 3.18.

Mass Spect: Calcd. Molecular Weight, 270.24.

Found, P7r0.

Infrared: The strong absorbance at 5.55 indicates the pres-ence of carbonyl fluoride groups. No absorbar.ceat 5.9 indicates the absence of the carboxylicacid group. (Figure IX).

23

C. 3,6-Bis (carbomethoxy)phenanthrene

The diester was prepared by adding excess ethereal diazo-methane to a slurry of the diacid (as received from AerojetGeneral) in ether. The ether was removed and the ester wasrecrystallized from etha.ol, m.p. 203-206°C.

D. 3-Carbomethoxy-6-trifluoromethyl Phenanthrene

Approximately 1 mg of the material giving the largest spot uponTLC of methanol treated run #30 was isolated by preparativeTLC (Mallinkrodt Chromar 1000, developed in 3:1 benzene Chloro-form). The infra-red spectrum (KB"' pellet) showed a carbonylband at 1715 cm- 1 and CF3 bands at 1320 and 1110 (or 1125) cm--.The mass spectrum of the same sample shoved a strong parention at the expected value (m/e 304).

E. Elemental Analysis - 3,6-phenanthrene Dicarboxylic Acid

Table V gives the data for the elemental analysis of two batches(AGC W71.3 nnd AGC W71.4) of 3,6-phenanthrene dicarboxylic acidalong with data furnished by Aerojet General Corporation.

24

VI. Analytical Procedure and Results - P-trifluoromethyl Toluene

A sample of p-trifluoromethyl toluene was isolated by distil-lation &nd characterized to be the pure compound by the followingdata:

Boiling Point - 0C 130.5 - 131.5 (Lit.(l) 129-130)

Refractive Index @ 24.5 0 C 1.4241 (Lit.(') 1.4276)

Infrared Attached as Figure IV

This sample •as used as an analytical standard for Gas Chroma-tographic analysis. Atcached as Figure V is the Gas Chromato-gram of the sample of ]p- crifluoromethyl toluene which was fur-nished to Starks Associates as part of this program. Figure Vincludes the pertinent data as to type of column, temperatureprogram, retention time anzd other parameters used to performthi3 analysis, The purity of samples 5043.26 and 5043.32, whichwere delivered to Walter Reed, were determined on the Gas chromra-tograph in a similar manner.

In addition to analyzing the purified product, the Gas Chromato-graphic analysis was extended for use on the crude reactor product.The relative response factor of p-trifluoromethyl toluene andp-tolulc acid fluoride to diethyl succinate was determined byusing pure samples. The diethyl succinate was then used as aninternal standard by adding a known amount to a sample of crudeand analyzing on the Gas Chromatograph in the same manner asdetailed in Figure V. For analyzing the crude reaction product,the analytical system had to be compatible with HF. A stainlesssteel syringe was used for injecting the sample and the columnwas originally chosen based on a knowledge that it was compatiblewith HF.

(1) Chemical Abstracts, Vol. 65, 18542, 1966.

25

VII. Analýtical Procedures and Results (3,6-bis(trifluoromethyl)phenaithrene)

A. Infrared Spectroscopy

All the infrared spectra were obtained by mixing the compoundin question with potassium bromide. The mixture was pressed intoa pellet form with a mini-press, and scanned with a Beckman IR-5Spectrophotometer. The spectra were examined for the presenceor absence oC the following strong and sharp identifiable bands.

5.50 - 5.60 -COF

5.75 - 5.85 -COCl

5.90 - 6.oo -COOH

7.50 - 7.60 -CF,4

8.90 - 9.00 -CF3

The following list itemizes the infrared spectra appearing inthis report:

3,6-Bis (tri fluoromethyl )phenanthrene Figure VI

3,6-Phenanthrene Dicarbonyl Chloride Figure VIII

3,6-Phenanthrene Dicarbonyl Fluoride Figure IX

3,6-Phenanthrene Dicarboxylic Acid Figure X

3,6-Bis ( tri fluoromethyl )phenanthrene-9-carboxylic Acid Figure XI

Phenanthrene Figure XII

Phenan.threnequinone Figure XIII

Crude 30 Figure XIV

An interpretation of the infrared spectra of crude samples 21-23,25-27, 30, 31, 35-37, 4i and 42 is shown in Table VI. The lastcolumn on Table VI is an attempt to Judge by appearance or ab-sence of certain infrared bands which spectra are closest to thespectrum of pure 3,6-phenanthrene dicarbonyl fluoride. The spec-tr•m that was the closest to 3,6-phenanthrene dicarbonyl fluoride

26

(Run #17) was arbitrarily assined the number .while thespectrum that was the further%:3t away (Run #20 - which showedno carbonyl fluoride bands and strong trifluoromethyl bands) wasarbitrarily assigned the number 14. The spectra assigned thenumbers between 6 and 9 are $he spectra of the crude sampleshaving the most product. Snectri' aisigned numbers 1 to 5 ap-pear to be from crude samples that were not fluorinated enough,while spectra that were aisigned numbers 10 to 14 appear to befrom crude samp~es that were fluorinated too strongly.

B. Ultraviolet Spectroscopy

The ultraviolet spectra were obtained by dissolving a weighedamount of the compourd in question with ethanol or chloroform.The solution was scanned with a Perkin-Elmer Model 202 U.V. -Visible Recording Spectrophotometer. The ultraviolet scanswere used to determine the extinction coefficients (k = A of

bcthe various compounds in question. In "Organic Chemistry" byCram and Hammond, published by McGraw-Hill, page 620 (1959),the absorptioa spectra of aromatic hydrocarbons are listed.The following table gives some of the extinction coefficientstaken from the above reference.

K K Kmax X max max

max Ab max Ab max AbAO mol-cm A0 mol-cm A0 moi-cm

Benzene 2,550 220 2,202 6,900 1,84o 83,000

Naphthalene 3,120 250 2,750 5,600 2,200 110,000

Anthracene ?,750 7,900 2,520 200,000

Phenanthrene 3,300 250 2,950 13,000 -,520 50,000

Naphthacene 4,730 11,000 2,'80 130,000

Pyrene 3,520 630 3,340 50,000 2,4OO 89,000

Chrysene 3,600 630 3,200 13,000 2,680 141,000

Azulene 6,070 263 3,41o 3,41o 4,360 55,000

Thus by comparing these extinction coefficients at the prescribedwavelengths one is able to determine if the aromatic ring in thecompounds in question has opened up or if it has rearranged to someother aromatic structure.

27

VJThe following list itemizes the ultraviolet spectra appearingin this report.

0.00000592 M 3,6-bis (trifluoromethyl)phenanthrene Figure VII

0.0000592 M 3,6-bis(trifluoromethyl)phenanthrene Figure XV

0.000652 M 3,6-bis (trifluoromethyl)phenanthrene Figure XVI

0.00000575 M 3,6-bis (trifluoromethyl)phenantbrene-9-carboxylic acid Figure XVII

0.0000176 M and0.0000439 M Crude 23 Figure XVIII

0.0000286 M 5022-19B (fraction from columnchromatography studies) Figure XIX

By studying the ultraviolet spectrum of Crude 23 one can observethat the extinction coefficients are not what they are supposedto be for phenarthrene type compounds. Thus one can conclude thatthere must be a large quantity of ring rearrangement or polymer-ization in this sample.

C. Gas Chromatography

Instrument: Loenco 160 Series

Carrier Gas: Helium

Column: 20' x 1/4" copper tubing packed with 30% SE-30 siliconoil on 60/80 mesh Chromosorb W.

Temperature: 300*C Isothermal

Injection Port Temperature: 300'C

Detector Temperature: 3000 C

Filament Current: 50 milliamps

Sample Size: 8A I

Recorder: Beckman 10-inch recorder with Disk Integrator

28

With the above chromatography system various samples wereanalyzed for product content. The product under these con-ditions eluted from the column after 11.9 minutes. A peakappearing at 5.9 minutes was identified as being a compoundhaving a phenanthrene-like structure with a CF group at boththe 3 and 6 ring positions. Further studies o? this compoundshowed that the ring protons in the 9 and 10 positions werealso substituted. With this chromatograph system variousoxher chromatographic peaks appeared out to twenty minutes,but these peaks were never identified. Figure XX shows agas chromatogram of a typical reaction run.

The samples were analyzed by gas chromatography by using aninternal standard technique. The internal standard used wasp-trifluoromethyl toluene (p-TFMr). This technique was de-veloped by the following method. A standard was prepared con-taining acetone ani weighed amounts of p-trifluoromethyl tolusneand 3,6-bis(trifluoromethyl)phenanthrene. When chromatographingthis standard with the present chromatographic conditions, p-trifluoromethyl toluene eluted from the column after 3 minutes.By knowing the ratio of the weights of the p-trifluoromethyltoluene and the 3, 6 -bis(trifluoromethyl)phenanthrene in thestandard, and measuring the area of the chromatograph peaks ofeach of these components in the standard, one is able to cal-c' late the responce of the one component relative to the otheron an equal weight basis. For example if the standard had beenprepared with 1.50 grams of p-trifluoromethyl toluene and 1.00gram of 3, 6 -bis(trifluoromet~hyl)phenanthrene and upon chromato-graphing this sample the p-trifluoromethyl toluene produced150,000 counts °while the 3, 6 -bJs(trifluoromethyl)phenanthreneproduced 71,000 counts, one could reason that since 1.50 granmsof p-trifluoromethyl toluene produced 150,000 counts then 1.00gram of the same material should yield 100,000 counts. Thus bycomparing 1.00 gram of p-trifluoromethyl toluene which gives100,000 counts to 1.00 gram of 3, 6 -bis(trifluoromethyl)phenesn-threne which gives 71,000 counts, one can say that the 3,6-bis(trifluoromethyl)phenanthrene gives 0.71 times as many counts,-s an equal weight of p-trifluoromethyl toluene. Experimentshave shown 0.71 to be the actual number for these studies. FigureXXI shows a chromatogram of the standard prepared by dissolvinga weighed amount of p-trifluoromethyl toluene and 3,6-bis(tri-fluoromethyl)phenanthrene in acetone. When a crude sample isreceived for analysis it is weighed into acetone along with aweighed amo•ant of p-trifluoromethyl toluene. This mixture is

29

then chromatographed. Again by knowing the ratio of theweights of the crude sample and the p-trifluoromethyl toluenein the mixture, and measuring the area of the chromatographpeaks of each of these components in the mixture, and alsoknowing that 3,6-bis(trifluoromethyl)phenanthrene responds0.71 times as much as p-trifluoromethyl toluene, one is ableto calculate the quantity of 3,6-bis(trifluoromethyl)phenan-threne in the crude sample. For example if the mixture hadbeen prepared with 1.00 gram of crude sample to be analyzedand 2.00 grams of p-trifluoromethyl toluene, and upon chroma-tographing the p-trifluoromethyl toluene produced 200,000counts and the peak corresponding to 3,6-bis(trifluoromethyl)phenanthrene produced 14,200 counts, one could reason thatsince 2.00 grams of p-trifluoromethyl toluene produces 200,000counts then 1.00 grams of p-trifluoromethyl toluene shouldyield 100,000 counts. Therefore, if the crude sample to besnalyzed was 100% 3,6-bis(trifluoromethyl) phenanthreneproduct, the peak cor:'esponding to the 3,6-bis(trifluoro-methyl)phenanthrene shoulJ give 71,000 counts. (Previouslyit was shown that 1.00 gram of 3,6-bis(trifluoromethyl)phenan-threne gives only 0.71 times as many counts as 1.00 gram ofp-trifluoromethyl toluene). Since the 3,6-bis(trifluoromethyl)phenanthrene gave only 14,200 counts, by ratioing this with71,COO counts, one can calculate that there is 20% 3,6-bis(trifluoromethyl)phenanthrene in the crude sample. FigureXXII shows a chromatogram of a weighed amount of p-trifluoro-methyl toluene and solvent extraction sample 26-4 dissolvedin acetone. This chromatogran illustrates some of the typicalpeaks which usually appear from various samples. The unknownpeaks are given a response of half as much and twice as muchas that of 3,6-bis(trifluoromethyl)phenanthrene. This givesan upper and lower concentration range for the unknown com-pounds. The upper and lower concentration ranges are thenaveraged, and this average number is the number which appearsin the reports for concentrations of unknown peaks.

This internal standard technique was uaed because it does notrequire the gas chromatographer to repetively reproduce sampleinjection sizes.

Table VII is a summary of the gas chromatographic analysis ofthe crude reaction products for all the rans after Run No. 20.

30

D. Nuclear Magnetic Resonance Spectral Analysis

The NMR spectra were obtained on a Varian Model A-60A spectro-meter. The samples were analyzed at room temperature instandard 5 mm. 0.D. semple tubes using tetramethylsilane asan internal standard. The sweep width was 1000 cps and thesweep time was 250 sec. Chemical shift values were obtainedfrom the precalibrated scale on the chart paper.

The NMR spectra proved very useful for identifications of pureor semi-pure materials. However, the crude reaction productscontained a wide range of materials giving such s'.milar NMRspectra that, in general, specific assignments were not possible.

The NMR spectrum of 3,6-phenanthrene-di-carboxylic acid (samplenumber 5022-8A) is shown in Figure XXIII. The broad peak at-5.0 ppm, which on addition of D2 0 sharpens and shifts to -4.0ppm, is assigned to the two acidic protons. The chemical shiftsof the 1,2 and 7,8 protons must be nearly the same since thespin-spin splttting, due to J12 and J 7 8 , is not observed in thespectrum. Hence, the peak at -8.2 ppm is assigned to the 1,2and 7,8 protons. The 9,10 protons are assigned to the singletpeak at -8.0 ppm. This leaves the singlet at -9.5 ppm to beassigned to the 4,5 protons. The above assignments are consistantwith the expected cbemical shifts due to the anisotropic ringcurrent effect in the aromatic phenanthrene rings.

The NNR spectra of the 3,6-phenanthrene-di-carboxylic acidfluoride are shown in Figure XXIV. The spectral assignments aresimilar to those for 3,6-phenanthrene-di-carboxylic acid exceptfor the absence of the acidic protons. The assignment is asfollows: the 4,5 protons are at -9.2 ppm, the 1,2 and 7,8 pro-tons are at -8.2 ppm, and the 9,10 protons are at -8.0 ppm.

The NMR spectrum of Crude 21 is shown in Figure XXV. The broadpeaks are apparently due to a wide range of products in thecrude. The NMR spectrum of Crude 30, which was a much higheryield reaction, is shown in Figure XXVI. The qualitative dif-ferences in the two spectra are quite apparent. The chemicalshifts for the 4,5 protons suggested that Crude 30 containedthree main components. This was later confirmed by G.C.-M.S.analysis.

31

E. Gas Chromatographic and Mass Spectral Analysis

The mass spectral (M.S.) analyses and gas chromatographic-mass spectral analyses (G.C.-M.S.) were performed using aPerkin Elmer Model-270 G.C.-M.S. spectrometer. A 6 ft. x1/8 in., stainless steel column, containing 5% SE-30 onChromosorb W, was used in the gas chromatographic sectionof the instrument. The G.C.-M.S. gas chromatograms wereobtained by recording the total ion current of the massspectrometer. The mass spectra were scanned in real time asthe peaks eluted from the gas chromatographic column.

The crude reaction products and starting materials were alsoanalyzed in the mass spectrometer using a solids probe tech-nique. This was ,recessary since the carboxylic acid fluoridederivatives would not elute from the gas chromatographiccolumns because, we believe, of their reactivity with the G.C.column packing. Also, we wanted to look for possible highmolecular weight materials of low volatility. The solidsprobe was initially inserted at room temperature and thenslowly heated to 2000C. Several mass spectrel scans weretaken as the temperature was increased. This allowed a partialseparation of materials due to the differences in volatilityof the various components in the crude samples.

In an attempt to obtain better quantitative data on the com-ponents in the crudes, the carboxylic acid fluoride componentswere converted into their methyl esters by reaction with methanol.The methyl esters were eluted and resolved without difficulty.The crudes were examined by regular gas chromatography usingflame ion detection (Beckman GC-5). The column was 6 ft. x 1/8in., stainless steel, and packed with 5% SE-30 on Chromosorb W.

The mass spectral data (solids probe) of a crude product areshown in Table VIII. The table lists only the more intense m/epeaks. The numbers in parentheses are relative intensitieswith the base peak assigned an intensity value of ten.

A G.C.-M.S. analysis was performed on Crude 26 for further elu-cidation of the reaction products. The total ion current chro-matogram is shown in Figure XXVII. The mass spectra were obtainedfor each of these components as they eluted from the gas chroma-tographic column. The m/e data for the more intense spectralpeaks are shown in Table IX.

32

The gas !hromatograms of Crudes 26 and 30 are shown in FiguresXXVIII and XXIX. respectively. These were obtained using theBeckman GC-5 chrcm-tograph with flame ion detection. As can beseen, the two chromatograms are siuilar. The main difference isthe much higher yield of 3,6-bis(trifluoromethyl)nhenanthrene inCrude 30.

The crude materials were treated with methanol in an attempt toobtain quantitative data on the reaction product by gas chromato-graphy. The gas chromatogram for the methoxylated Crude 30 isshown in Figure XXX. The two new peaks have been shown by G.C.-M.S. to be the methyl esters of 3,6-phenanthrene dicarbonyl fluor-ide ad 3-(trifluoromethyl)ph-nanthrene~6-carbonyl fluoride. An

estimate of component concentrations based on peak heights in crude30, gave 13% 3,6-bis(trifluoromethyl)phenanthrene, 40% 3-trifluoro-methyl phenanthrene-6-carbonyl flucride, 23% 3,6-phenanthrene di-carbonyl fluoride, and 24% other materials. The percentages werecalculated assuming equal detector sensitivity for all samplecomponents.

F. Thin Layer Chromatographic Analysis

A survey of thin layer chromatographic systems showed that theproduct, 3,6-bis(trifluoromethyl)phenanthrene could be resolvedfrom other materials formed in the runs under the following con-.ditions:

Plates: E. Merck 4GF, 250 micron

Activation: none

Solvent: Cyclohexane-carbon tetrachloride 1:1 by volume

Development: 15 cm

Visualization: Fluoresence quenching

Sample size: Sufficient to contain I/A to 1 microgram ofproduct.

Improved resolution for quantitative work (v.!.) was obtained byemploying 4:3 cyclohexane-.carbon tetrau~l~lride and developingplates twice. Figure XXXI shows the TIC plate for a known se•npleof 3,6-bis(trifluoromethyl)phenanthrene and several crude reactionproducts.

Samples of the intermediate product, 3,6-phenanthrene dicarbonylfluoride (product from run 17) could not Oe moved from the originregardless of solvent polarity up tairough acetonitrile. This be-havior indicated acylation of the plate, and the acid fluoride

33

groups were converted to methyl ester groups by reactionwith methanol using pryidine catalyst. A 5 to 30 mg samplewas accurately deighed and added to 3.00 ml methanol alongwith an amount of pyridine approximately equal in weight tothe sample. The solution was warmed in a closed containerfor two hours and thence used directly. The conditions usedfor chromatography were as follows:

Plates: E. Merck 4GF, 250 micron

Activaticn: none

Solvent: Benzene-chloroform 3:1 by volume

Development: 15 cm

Visualization: Fluorescence quenching

Sample size: Sufficient to yield 0.2 to 2 microgramsubstance.

The bis-trifluoromethyl product was unresolved from unidentifiedmaterials in the latter solvent system, but 3,6-bis(carbomethory)and 3-carhomethixy-6-trifluoromethyl phenanthrenes were wellseparated from each other and from extraneous materials. Two-fold development was utilized on quantitative runs. Figure XXXIIand XXXIII show the TLC plates for L known sample of 3,6-bis-(carbomethoxy)pl.enanthreile compared to the methoxylated reactionproduct for several reaction runs.

No attempt was made tc achieve comvlete and reproducible satura-tion of dpveloping chambers. Because Rf values are not exactlyreproducible under these conditions, known standards were run onevery olate.

Quantitative mneasurementGs were made with a Farrand Optical Co.Chromatogram Scanner. A peak area vs. quantity curve was gener-ated for each plate by including 3 or 4 standard samples straddlingthe unknown. Measurement wns by IN absorption and was made at thefollowing waelengths:

3,6-W •.ri fluoromeihyl )phenanthrene 250 rim

3,6-bis earbomethoxyv)phenanthrene 315 nnm

3-carbomethoxy 6-trif'iuoromethyv] rhenanthrene 315 nm

34

Since a standard sample of the last compound was not avail-able, approximate assay was made by using the peak area vs.amount curve for the diester. Because the diester Amax(315 nm) is longer than that of the mcnoester (295 nm), thisassumption probably led to low results. Attached in Table Xis a summary of the quantitative results obtaiaed for Runs30, 37, 41 and 46. Table Xi summarizes the qualitative ob-servatiors for a number of other runs.

G. Solvent Extraction Studies

In an attempt to sep, L components by their solubilitydifferences in various solvents the following extractionswere carried out in soxhlet extraction apparatuses.

1. A 4.oo gram sample of 3,6-phenanthrene dicarboxylicacid was extracted with 300 ml of acetone fo,- 18hours. Reweighing the material in the Soxhletextraction thimble showed that 3.20 grams stillremained unextracted.

2. A 4.00 gram sample of crude mate:rial from Run #17(which was later shown to be essentially pure 3,6-phenanthrene dicarbonyl fluoride) was extracted with300 ml of acetone for 6 hours. Reweighing the ma-terial in the Soxhlet extraction thimble showed that1.30 grams still remained unextracted.

3. A 4,02541 gram sample of c'..de 23 was extracted suc-cessively with heptane, tenzene, diethyl ether, andacetone. Figuý'e XXXIV shows a flow sheet of Thisextraction. After each extraction fraction was col-lected and dried, it was weigned, gas chromatographed,scanned on an infrared spectrophotometer, and meltingpoints were determined on some of the fractions. Theheptane extraction recovered 44.9% of the productmateriel known to be in the starting sample of Crude23, while the benzene extraction recovered 39.5% of theproduct material (•,6-bis(trifluoromethyl)phenanthrene)known to be in the starting sample of Crude 23.

4. A 4.73280 graz. sample of Crude 25 was extracted underthe same conditions as was Crude 23. Figure XXXV showsa flow sheet of this extraction. The heptanc extractionrecovered 57.1,j' of the nroduct material known to be in

the starting s8azple of ('rude 25, while the benzeneextraction recovered 2I.0". of the product material(3,6-bis(trifluoromethyl)phenanthr'ene) known to be inthe starting sar.ple of ,-rude 25.

5. A 3.49667 gram sample of Crude 26 was extractedunder the same conditions as was Crude 23. FigureXXXVI shows a fl.ow sheet of this extraction. Theheptane extraction recovered 59.7% of the productmaterial known to be in the starting sample of Crude26, while the benzene extraction recovered 23.7% ofthe product materiaJ (3,6-bis(trifluoromethyl)phenan-threne) known to be in the starting sample of Crude26.

6. A 1.10127 gram sample of Crude 27 vas extractedunder the same conditions as was Crude 23. FigureXXXVII shows a flow sheet of this extraction.

7. A 3.42999 gram sample of Crude 30 was extractedunder the same conditions as was Crude 23. FigureXXXVIII shows a flow sheet of this extraction. Theheptane extraction recovered 84.0% of the productmaterial known to be in the starting sample ofCrude 30, while the benzene extraction recovered1.7% of the product material (3,6-bis(trifluoro-methyl)phenanthrene) known to be in the startingsample of Crude 30.

8. A 1.9636 gram sample of Crude 31 was extracted underthe same conditions as was Crude 23. Figure XXXIVshows a flow sheet of this extraction.

Summarizing these extractions shows that by extracting withheptane or benzene most of the 3,6-bi(trifluoromethyl)phenan-threne can be extracted from a crude mixture. Also from study-ing the infrared spectra of the heptane and benzene extractfractions it appears that some of the 3-trifluoromethyl phenan-threne-6-carbonyl fluoride 3-trifluoromethyl phenanthrene-6-carbonyl fluoride also appears in these extract fractions.

H. Column Chromatography

Col,=n chromatography was also used in an attempt to separate thevarious components in each sample.

In this experiment 4.oo grams of Crude 21 was extracted witi; 300ml of acetone in a Soxhlet Extractor for 18 hours. The acetoneextract was cooled, and then evaporated leaving 3.60 grams of ashiny brown residue. A slurry containing 2.20 grams of thizresidue mixed vith 20 ml of heptane was placed on the top of achromatograph column. The 16" x 3/4" column had been orevio--slypacked with Silica Gel which had been activated at 107;C for 2

36

hours. After the sample was placed on the column, the columnwas successively washed with heptane, various eptane-chloro-form mixes, chloroform, various chloroform-acetone mixes andacetone. The samples eluting from the column were collectedin 200 ml fractions and evaporated. They were then weighed,and the larger samples were scanned in the ultraviolet andinfrared regions as well as gas chromatographed. Figure XXXXshows the chromatogram obtained by plotting weight of eachfraction collected versus the order of elution of the fraction.At the top of the chromatcgram is listed the solvent used toelute each fraction. Of the total of 2.20 grams placed on thecolumn, 2.1137 grams was eluted and collected off the columngiving an accountability of 96.1%. Table XII lists some ofthe characteristics of the larger samples collected from thechromatograph column. Sample 5022-19B contains the largestpercentage by weight of product, while samples 5022-19G, -19Kand -19M probably contain a large quantity of 3-trifLuoromethylphenanthrene-6-carbonyl fluoride. The ultraviolet studiesshow that sample 5022-19B contains the mcst phenanthrene ringcharacter while samples coming off the column later show lossof the phenanthrene ring character.

37

VIII. Conclusions and Recommendations

P-Trifluoromethyl Toluene Studies

1. Reactions studies in the 300 ml and 1750 r-l autoclave showedthat a 75-80% yield of p-trifluoromethyl toluene in the crudereaction mix can be obtained by reacting p-toluic acid withSF 4 under the following set of reaction conditions:

SF4 concentration - 50% molar excess

Temperature - 160-170'C

Time - 16-18 Hrs.

Pressure - 2,000-2,500 psig (autogeneous pressuredeveloped by adjusting quantity ofreactants to reactor size)

2. A yield of '95% for crude p-trifluoromethyl toluene can beobtained under the above conditons of p-toluic acid fluorideiv recycled. Studies to determine the feasibility of recyclingthis material should be made to determine the optimum yield.

3. Recovery of Y99% purity p-trifluoromethyl toluene from thecrude reaction mixture by d!'tillation was 90% of that indi-cated by the analytical data.

4. The average overall recovered yield of P99% purity p-trifluoro-methyl toluene based on the p-toluic acid charged was 63.5%as determined by the combination of six runs In the 1750 mlreactor.

5. A minimum temperature of 1401C was required to make the reactionproceed beyond the acid fluoride to the trifluoromethyl functionin any significant yield. This situation relates to using SF 4without any catalyst.

S}Ff was shown to have a significant catalytic effect upon thereaction of SF 4 with the p-toluic acid fluoride. At 1400C, noreaction to the trifluoromethyl function was observed withoutHF while a 76% conversion was obtained at the same temperaturewith HF (equal molar quantity to that of p-toluic acid). How-ever, HF was not shown to be a beneficial catalyst when workingwith 3,b-phenanthrene dicarboxylic acid as it promoted undesirableside reactions.

38

7. The presence of large amounts of S2 F2 (>10%) in the SF4 producesdecomposition products and none of the desired product. An S2 F2ýevel of <2% in the SF4 was acceptable. This data was developedwith the p-toluic acid reactions and it is expected that similarresults would be obtained in the 3,6-phenanthrene dicarboxylicacid reactions.

8. A corrosion rate of '0.002 inches/year for 316 stainless steelwas determined under reaction conditions, indicating that 316stainless steel is a suitable material of construction for usein these reactions.

3,6-Phenanthrene Dicarbox~lic Acid Studies

1. Reaction studies in the 300 ml autoclave showed that a 22% con-version to 3,6-bis(trifluoromethyl)phenanthrene could be obtainedby reaction of SFh4 with 3,6-phenanthrene dicarboxylic acid in thepresence of an inert solvent. An additional yield of 2.4%3,6-phenanthrene dicarbonyl fluoride and 17.5% 3-trifluoromethylphenanthrene-6-carbonyl fluoride (intermediate compounds) wasalso obtained with the remaining material unidentified. Theseresults were obtained using the following reaction conditions:

Temperature - 210 to 2200C

Pr-ssure - 1950 to 2150 psig

Reaction Time - 16 hours

SF4 Concentration - 1100% excess

Solvent - Benzotrifluoride (3 parts [by weight] to 1 part3,6-phenanthrene dicarboxylic acid)

A similar reaction performed at a lower temperature (180'C) gavea lower conversion (8.1%) to 3,6-bis(trifluoromethvl)phenanthrenebut a higher yield cf the intermediates (48% 3-trifluoromethylrhenanthrene-6-carbcnyl fluoride and 26% 3,6-phenanthrene dicar-bonyl fluoride).

2. Further reaction studies should be conducted to study the effectof temperature between 180 and 220 0 C and also the type and concen-tration of solvent in order to optimize the yield of 3,6-bis(tri-fluoromethyl)phenanthrene while keeDing the yield of intermediatecompounds as high as possible.

39

3. Studies to 6etermine techniques for isolating and purifyingthe desired compounds from -he reaction mixture should bemade to substantiate the analytical yields presented above.

4. Relatively pure (>95%) 3,6-phenanthrene dicarbonyl fluoridecould be produced in quantitative yields from th" 3,6-phen-anthrene dicarboxylic acid by reaction with SF4 at temperaturesof 1i0 to 160oc.

5. Studies on optimizing the SF 4 used in these reactions should bemade, since the excess quantities used in these reactions wouldmake the process commercially uneconomical.

6. The use of HF as a catalyst was showir to be detrimental vhenused at elevated temperatures in molar quantities greater thanthat generated during the conversion of 3,6-phenanthrene dicar-boxylic acid to 3,6-phenanthrene dicarbonyl fluoride. Furtherreactions using smaller quantities of HF or reactions using acombination of 3,6-phenanthrene dicarboxylic acid and 3,6-phen-anthrene dicarbonyl fluoride should be investigated.

7. The sensitivity of the 9 and 10 hydrogen to reaction was shownas substitution will occur at these positions under certainreaction conditions, particularly in the presence of HF atelevated temperatures.

8. Economic evaluaticn of this process based on a 20% conversionto 3,6-bis(trifluoromethyl)phenanthrene and an overall 50% yieldof 3,6-bis (trifluoromethyl)phenanthrene plus intermediatesshowed that a selling price of %$15 per pound could be achievedat production rates of 30,000 to 50,000 lb/yr. For smaller re-quirements, such as 3,000 lb/yr 3,6-bis(trifluoromethyl)phenan-threne, the selling price would be $40/lb. These figures do notinclude the cost of 3,6-phenanthrene dicarboxylic acid, whichshould be added at 1.9 times the per pound cost of 3,6-phenan-threne dicarboxylic acid.

40

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Table V

Elemental Analysis of3,6-Phenanthrene-di-Carboxylic Acid Starting Material

B~tch AGC-WTI.3' Batch AGC-WT1.4 Batch AGC-WTI.4(2)

% Carbon 69.88 70.61 71.41

% Hydrogen 4.28 3.77 3.94

% Nitrogen Trace (0.1-0.3) Trace %.0.3%) 0.61

% Chlorine 0.88 0.08

% Ash 1.46 0.32

Major Metals(1) Fe, Cu, Na Fe, Si, Na Na dO.l%('0101%)Minor Metals Mg, Si Mg Cu 4 5 ppm('0.01% & >o.oool%)Trace Metals Mn, Ag, B, Ti, Sn, Cu, Ag, Mn, Fe, Mg, Al 41 ppm(<0.0001%) Ni, Al, Ca, Cr Ti, Ni, .A1, Ca

(1) Arc emission spectrographic nalysis of the ash.

(2) Data supplied by Aerojet-C" heral.

45

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Table VIII

Solids Probe Mass Spectral Data for Crude 26

Probe

Scan Temp. Major m/e Peaks

1 750C 270(6), 292(8), 314(lO), 348(8), 350(6), 382(5), 388(4)

2 1200C 292(10), 314(10)

3 1500C 292(10), 314(9), 348(6), 382(5), 388(4)

4 175 0 C 264, 270L, 292, 314

5 210 0 C 243, 251, 345, 518, 586, 614, 633, 634, 635, 636, 655,656, 657, 658, 666, 688

Expected Intermediates and Product

C0 CF3C I

C=o CF3 CF3

F

Mol. Wt. 270 292 314

Possible Substitution Products

SF2 F 2

CF3 CF3 CF3

CF3 CF3 CF3 CF3

346 3d2 382 388

48

Table IX

G.C.-M.S. Analysis of Crude 26

G.C. Peak Major Mass Peaks

8 339, 348, 350, 369, 388

10 350, 363, 382

12 314

14 296, 311, 327, 346, 348

49

Table X

Thin Layer Chromatography AnalysisQuantitative Results

3-Carbomethoxy-3,6-Bis (trifluoromethyl) 3,6-Bis (carbomethoxy) 6 -trifluorometRun Phenanthrene Phenanthrene Phenanthrene• iNo. - % -% %_ ,

30 (Solids) 7.5 26 4837 (2) 1.3 6.5 6.8

37 (Solids Basii) 4.6 26 2741(2) 6.7 0.6 4.8

41 (Solids Basis) 2.4 17.5 22.5

46 (Solids) 4 1 33 8

(1) Assay depends upon assumption of calibration curve for 3,6-bis(carbomethoxy )Phenanthrene.

(2) Analysis of reactor effluent including solvent.

50

Table XI

Thin Layer Chromatography AnalysisQualitative Observations

Legend

b-TFMP - 3,6-bis (trifluoromethyl )Thenanthrene

DME - 3,6-bis (carbomethoxy)phenimthrene

TME - 3-carbomethocy-6-t rlrluoromethyl phenanthrene

X - Spot faster than b-TFMP in cyclohexane - carbon tetrachloride

Y - Spot slower than b-TF.MP in cyclohexane - carbon tetrachloride

Z - Spot slightly faster than TME in benzene - chloroform

Run 26 - Contains 3,6-bis(trifluo:omethyl)phenanthrene and similar amountsof X and Y. Methanolized mixture contains trace DME and smallamount TME.

Run 30 - Contains 3,6-bis(trifluoromethyl)phenanthrene, trace X and no Y.Methanolized product contains substantial DME and TME.

Run 31 - Trace 3,6-bis(trifluoromethyl)phenanthrene, small amount X, no Y.Methanolized product contains more DME than 30, less TME.

Run 35 - Methanolized product contains trace DME, trace TME, no observable3,6-bis(trifluoromethyl)phenen+threne and substantial X and/or Y.

Run 36 - Methanolized product contains less DKE and TME than 35 and sub-struntial X and Y.

Run 37 - Contains some 3,6-bis(trifluoromethyl)phenanthrene. Methanolizedproduct contains DME and TME and some Z.

Run 41 - Contairs substantial 3,6-bis(trifluoromethyl)phenanthrene and large

amount X. Methanolized product contains trace DME and amount of TMEsimilar to 37.

Run 45 - Much X, obscures any 3,6-bis(trifluoromethyl)vhenanthrene present.Methanolized nroduct contains no DME or 'ME but substantial Z.

Run 46 - Contains trace 3,6-bis(trifluoromethyl)phenanthrene and trace X.Methanolized product contains much DME, some TMR and some Z.

51

L

0) FA FA m) toU) U)

0 t

0 I 02 m U 0)

ýHi

-4 0H~P42

4

\0

0 C~0

04 m \.D .l0 r4 CC)

E-4 &4

0~

om H~ CU 4 N cL U 4

4-4)

_:rCr (Y -4 M

bC 4.)H\, O H O\ -H\ HOrH UH -r4 C-UHI0 4 C- U4) )

.- 4) C) =G = 04.) > D = - U t- U 1- 6t- m~ )uU 0:j H- L)C) U U u U H- be'S0 VA VA UA 0 SV)~ t- VAX L0 00" u0 r. V r 0 0

u Lr'., (V C\ N. LC..4 tl U4 I LA.,4+3

be ()CU 0 H- L ON Cr)

39 0 0 0 0 0 0 0

4 1- H -4 -4 HH

4) cUi CUl CUj CUi CU C CUI mN. NU C CUj CU CUj CUj CUj1

-J0 0 0 0 0 0 c 0

U-1 rl\ N Ln U-\ r\ U\ UI

FORM NO, 8100 a

BY DATE .IN.C. SHEET NO. OF

SUBJECT .. JOB NO.

FIGURE I

& REACTOR FLOWSHEET300 cc AUTOCLAVE FOR SF4 SYNTHESIS STUDIES

0 - 3,000 Psi

SIIHigh Hig

Pressure PressureValve Valve

Mi, 900 Polyethyleneml of Bottles20% NaOH

/ -- . D. clD-- - -- - - - 3 , 0 0 0 p s i S c a l c

) Heated

Autoclave

Cauge

Dry Ice Variac VertAcetone

Bath

VacuumPump

NOTE:

1. All piping,valvlng and connections in high pressure section tc be ratedat a minimum of 5,000 psi.

2. System to be testec with N2 2 ?,500 psi and 1900 C.

53

tt

- t

f +H-4

i- 41

T- P4 -14

Zu0 :2 1

0 14 -r-t

k

0-, -4T

4J 9 .

ýq -:jý-- -r4 0 H H m

t 0 WVg2 IM4 p4

0 0 C.) 0 0ai> 0 0 FH -t OL4

_a 0 4

41_ :_ -L9

PT4T CY

:1 ~Figure III -

41 ~ :1-SF 4 Synthesis with Tj~1,800P-Toluic Acid

4...~ L Temperature-

* vsPressure -

1i,64oo- Run #13 (Acid Fluoride)

1,600 ~0 Run #15 (Acid) .f.

1414-

1,4o

-4-j< f ~ .- - rj

-~ t

8000 444 .~LhA -

N~ 44 ti r :

jF 4",

i-14 -4

400

3 100 ~emp-OF "CO 300)

-... ... ...

... .....

... ......T...~ ~ ~ ... ...

.... .. ..

. .. .. .... . .. .. .. ...

C, -Lý -,-L4L4

f4I .~ 04 0 '-4 00 0 0OD .4 40 lw1

.2is.a. " EI <74' 1,.. -

NO. in -qII- - 2,

4-s

4- 4- 10 .

:1.b V__14JK

612 2 C !1 2 92 0

it u

.. ........ .j1H 2 2 2

o oU

I ml

T MT

a U,

44 - -ý-4++++ +4O

CL) U U

'~~~ ý::2 t 4

40 +

T T I

44n

i + L A -

6666oI T Io- -~m~vs~osZ

~I "t I t f

"IL

22

i 4 _3 .........V

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o v W)' NmvW> ......OO -r-tor

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41 00

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____________________M _ 4

+00000~)NV~SSVF6

.. .... O.) .. . . . . ..

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ui.

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0~~~ 0Ot MVt

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00

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II

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46

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+ Iý

olt',

- - - - . .,

0 M:7t7T77

wit.

-I t -

Gas Chromj0 5 r..m

~~~a one v~~~h1 hu~r

HtJ@r744t ~t,5 otq~

7- s .

6~rm6

I[11 I I! fill m60

I I I N i

IL I4 0i

I I-L-- - - - - -

2- T 4 - - - -0

TTT~-I- R V------ - -

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r4 Tf -4

'H~~T J- I 777

-~VI 4--- ---

II , Al - - '1 T

lit~~li I-- ,

- I f il I Ii 1

*I I * I _

-500 -400 -3001

FIGURE flCIIT

SAMPLE: rn

C=

I .OH

Sample Number: 5022-8A

Sweep Width: 1000 cps

Sweep Offset: 0.00 cps

5022.8A + D2 0

5022-8A

"- Solvent: DtO-d 6

-6 .0

I. 1 A --A A -*I.--8 . 0 P- 5 6 . 0 -4 . 0

-5f0 -'400 -300

FIGURE XXIV

Solvent: THF

II&/JK 191-139 F

c=O

FSample, Number:`-. 131-139F and SF4 #17Sveep Width: :100•.cjs•

Sweep Offset: 0.000cps

(Solve'nt : THY) ,._

A!

-8.0 -6.n -11.0Fl~. 76

-600 -0 0

FIGURE XXV

Ether extract*

of Crude 21

DM.S - 6 sovph

Ssmple: Crude 21Sweep Width: 1000 cps§wee'p Offset: 0.00 cps

Solvent: r MSO -d6

Lrude 21 jkAl

CDC1 3 solvent A?"~

Solvent: CDCl3

-10. ) .-0

FIGURE XXVI

Sample: Crude 30

Sweep Width 1000 cps

Sweep Offset: 000 cps

Crude 30 + D 0

(So]v.nt-: DMSO -d6,Sweep Width: SOO 41s,/

I t.

-8.0 -6.0 .4.0

PPM

78

FIGURE XXVII

Sample: Crude 26Column: 5% SE-30 .,, C'hromosorb W

Program: I00°C-225*C 4 °/min.

-~~.

4ji

h:0zx

L

I .......-

--.i• :: I--.

--- , !i.i:*--V-*-•----

-- * --I--

2..

.

=

1-7- --

7771 -

-.-

7

---

a)---

•-- --I i

:!--

-I .-...-.....

'- !--

S......:11--

:. ..-

-...

-......

'-.I---.....-.

-

-,

I

t-

"- --

r

li--21:..

., .

-

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.77.' '-'' -

79

001 (36 -0.1 0 01; '

001 06 09 OL 09 01'Ot

001 06 0r. 04. 09 09 01'

001l 06 0O OL 09 09 O

001 06ý 0o 0-1. 9 0 0.1

001 0!,C C'

00 09, or 01 a

at 09 09 ow oa 0, 0

OL ~ ~ ~ ~ 09 O. o o t J0

ot 09 Or i l

I06 010 O 0 O

001 06 009 0!, oz 9 09 0

I' 7

001 06 09 0 4 09 0 -- O

0ct 06 09 04 09 0ll ov

Figure XXXI

T.YC Analysis3,6-Trifluoromethyl Phenanthrene

and Crude Reaction Products #26, 30, 31, 35, 36Cyclohexaie - CC14 Solvent

I I,I [•--Ortgin

r4f Cm rn Cm m1I I - 4 0 I

f. 4 4 r1 ED 4 3 r I

rl IC

P.

0

413

4.)

"0

F~igure XxxiI,

TLC Analysis3, 6-bi s-Trifluoromethyl Phenanthreneand 3 ,6-bis-Carbomethox~y Phenanthrene

and Methoxylated Reaction Products #26, 30, 31Benzene-CHC13 Solvent

3:1

+-Front

-3 )6-Bis-TrifluoromethylPhenanthrene

f-3-Trifl~uoronmethyl-6-Carbomethoxy

Phenanthrene

-3 ,6-Bis-Carbomethoxyr Phenanthrene

f---Origi n

o 0 00 0 C 0

I In I q

'- H 4 0 0 4)

"4 00

Figure XXXIII

TLC AnalysisMetho-ylated Reaction Products #17, 30, 35, 36

Benzene-CHIC1 3 Solvent2:1

7)

'*• 3 ,6-Bis-TriflaoromethylPhenanthrene

S* 4r-- 3,6-Bis-CarbomethoxyPhenanthrene

f-- Origin

Note small

Remainders -.- en H

at originin 35 & 3u

C.) C.) C) C) .0,

~ J\ C.

S-,Khl,,t Extr aml an , fk{140

;# % 614"'e P- Cool to i r~ teli. F

sitrk'%63 10 "- -tei-.2, 10o4 Wk12 C

r 1%bs 23- 4 M, 72-198 "C

Nietsto a 61,ri o, s54

!klcj~ OA A 1AVr

-.4t' 3w -Ilk

4, 10 ý.M'.r

44 ~ 0 0 044 _

I I0.ji ~ .

-0 4e Th e c n r du t s ae0n e ch a p e t r t o

reer to% th ecetg f ,-iotilooieh

NtzT*phercenthn product stten each nivdanle fraction.

86

Sv)%Nkt Edr&citorn wst 30C mi. C,)41b

0. 5(.016 51,S K*.4 (ia2

SuA~dt ejdad%, u~i~ 64a~fok~t %a-A air

~oO p4 C~46 4r0-3363 515 NcIIi- Scig 0,%~95(,

U0. T~

.2, ~ ~ ~ ~ ~ ~ Ea 18o40 et ~ . P16 0 CY10 '4

3"Al~ 4mh, WA -*w^fal;

310 ,1~. At4iE11 A,*0K2ý r

4or 18l~r

0, 1T

2.17

re~i 3ccX j If +litdfw4, Oirl

OmA-tlq for I0.1410

I t tt.338 :r. a-

D~~ ~0oX ProJ.

Note: The Percent product stated on each ample traction reter, to the

percentage o: 3.6-bim(trifluorcmeth3?l)phevnathreon found in eachIndividua~l fraction.

2 (v

%Sro c riomi

'9 ~~~~~ Coal W t-~e~r

Sudle eprot'ol 44j 300 ,,1 So 16CI.Hb~11 i%.. 8 '%rS p

Iowa~1~o 141q %,

i919-0- 5".. Me 7'*ý~e~

O.0b20T

Nots hgpecet rouc matd n ac cmp. ratin et~mtotS

indiehirae.1 tractio

88ý0 3 1 %%.Sok

0.1 yeF0

F "~~I Cool +0 wotcf- I C ev

rt ~ ~ ~ ra~ in nC- t4O

0.2 72~o, ;95a 6j 18 P 93-1r %.

27-Z t

I.;0 '0

*.g- 18 >ýO~rs

&.c-74o 7) , ut I e

(" 410 . -

+k 4 I A$IVON .Q111 . S0.~f' 0 I

~4.0 z .tJ

Noe Th ecnIrdutsae neahsml rcto eest

the pecnae f 36bi~rfuooehldhn(hrn onin %ec Odv~ulfacin

It

No.:Th prcatpr4ac satd n1ac a15e6 (ra52.9r7.r)t

th@ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ c r~cna f36butilorsthlpeatrn on[1, 6nb i d v i143 r9 ton

ý f 3o-

Cra. , 3L/ ,. JrBr- S-Iý AFV rW4C;"/dA.' SO7&- P'Er.

0.•1 . P-o

03"3-13 ,,j. e~ -K+, tS1,.43733 ~ ~~~~~ ~.X

It I0,o3;3q (a,• Io~

O. 23504'3V-2

*1 4 " .37719

0~~ ~ ~ / 0 P-04 4 8

0..' ..

O.,-Iq _ I2 Io,~ .,,,

'S .% O S.,r,% .I

4ýS +Imoft

Note: The percent product stated on each sample fraction refers to thepercentage of 3,6-bis(trifluoroaethy1)phenanthrene found ineach individual fraction.

91

0

I f IU-H

C~C,pI\

44

0 0

FIGURE XOXXXI

Proposed Production ProcessSF4 Reaction with 3, 6 -phenantbrene dicarboxylic aoid (PDCA)

PDCA Conversions

20% to 3, 6 -bis-(trifluoromethyl)phenanthrene (b-TFMP)20ý to 3-(trifluoromethyl)phenantnrene-6-carbonyl fluoride

(TFW-CF)10% to 3, 6 -phenanthrene dicarbonyl fluoride (PDCF)

Recycle Conversions

80% TF'e-CF to b-TFMP80% PDCF to b-TFMP

SF4 Conditions

50% excess with 95% recovery

,,16o lb, SFh-

350 lb. SF:h Recovery

SSF4P•SOF2 _

HF

190 lb. PTCA stainless 100 1b. b-TFMP Extraction 100 lb. Recrystalli- 100 lb. b-T'MPsteel 42 lb. TFMP-CF b-TFMP zationi autoclave 19 lb. PDCF

42 lb. TFMP-CF19 lb. PDCF

42 lb. TFMP-CF ExI19lIT PDCFEtrcin

93

Securitv Classification

DOCUMENT CONTROL DATA.- R & D(S~curlty cleasification of title, body of abs tract and Indexing annotation must be entered when the overall report Isca sild

I. ORIGINATING ACTIVITY (Corporate author) lIa. REPORT SECURITY CLASSIFICATIONAir Products and Chemicals, Inc. Unclassified

F P. 0. Box 5382.GRUAllentown, Pennsylvania 18105

3. REPORT TITLE

SYNTHESIS OF P-TRIFLUOROMETHYL-TOLI JENE AN~D 3, 6-BIs (TRIFLUOROMETHYL)PHENANTHRENE USING SULFUR TETRAFLUORIDE

4. DESCRIPTIVE NOTES (7yp* of report and inclusive &eto@)

Final - July 1, 1969 to February 1, 1970S. AU THORIS) Pirst nome,middlueinitial, last namte)

Andrew J. WoytekJames F. Tompkins

0. REPORT DATE 7a. TOTAL NO. OF PAG*:S ___176 NO. OF REOPS

April 1970 97S14. CONTRACT OR GRANT NO. S.ORIGINATOR'S REPORT NUM'SERII(S)

DADA-l7-70-C-0007 8'720b. PROAECT NO. 8--0'

C. Sb. OTHER REPORT NOMS (Any other numnber@e& tatmay le aaelo~edthi. rviport)

10. OIST`1111RIUTION STATEM4ENT

* Distribution of this document is unlimited

IIIt. SUPPLKMLNTARY NOTES 12. SPONSORING MILITARY ACTIVITYD~epartment of Organic ChemistryDivision of Medicinal ChemistryWalter Reed Army Institute of Research

__ __._ __ __ __ __ __ __ __ __ __ __ Washington D. C. 20012

The object of this work was to investigate, or. a laboratory scale, the individ-ual reactions Of SF4 with p-.toluic acid to produce p-trifluoromethyl tolueneand of 3,6-phenanthrene dicarboxylic acid to produce 3,6-bis(tri~fluoromethyl)phenanthrene. This laboratory data was to serve as a basis for scaleup ofthis reactions to a commnercial process.

A total of 4~6 runs were conducted during this investigation with 16 runs per-formed with p-toluic acid in a 300 ml autoclave, 10 runs with p-toluic acidin a 1750 mli autociave, and 20 runs with 3,6-phenanthrene dicarboxylic acidin the 300 ml autoclave. The parameters investigated were temperature overthe range of 20*C to 225'C, pressure over the range of 1i40 to 3,000 psig,reaction times from one to 18 hours, SF4 concentrations at 50% to 4,500%excess, catalysis with hydrogen fluo.ride and the use of' inert solvents forthe 3,6-phenanthrene dicarboxylic acid runs.

The p-toluic acid reaction was initially studied in a 300 ml hastelloy auto-

condtios o 160C,160 psg, 6 hur eaciontim wih a50%molar excessof S4. ecyle f te p-oluc aia luoide eneate duingthis reaction

would increase the yield of p-trifluoromethyl toluene to over 95% for theseconditions. This reaction was scaled to a 1750 ml stainless steel autoclave

DD ~ ~ ~ ~ Fe ?.17 utIeno:ma?. I JAN SC. UNIC04 IS11DD ,,,4 3w1"Ate "ie 95 Secrity Classific.Uws

Continuation of Document Control Data - R&D

in which a total of ten runs were made. The conversion to p-trifluoro-methyl toluene using similar reaction conditions averaged 72% (57 to 85%range) for these runs and the yield averaged 87% (77 to 100% range) in-cluding recycle of the p--toluic acid fluoride. Purification of the cru.6ereaction product by distillation gave a 90% recovery of r99% purityp-trifluoromethyl toluene from the reaction mixture. From this seriesof reactions, two 1500 grams samples of p-trifluoromethyl toluene wasdelivered to the Walter Reed Medical Center.

Twenty reactions of 3,6-phenanthrene dicarboxylic acid or its derivative3,6-phenanthrene dicarbonyl fluoride were performed in the 300 ml auto-clave. Relatively pure (795%) 3,6-phenanthrene dicarbonyl fluoridewas produced in quantitative yields from 3,6-phenanthrene dicarboxylicacid by reaction with SF4 at temperatures of 110 to 160 0 C. The highestconversion (22.5%) of 3,6-bis(trifluorumethyl)phenanthrene was obtainedby suspending the 3,6-phenanthrene dicarboxylic acid in benzotriflu~rideand reacting at a temperature of 210 to 220'C, pressure of 1950-215"psig, reaction time of 16 hours with a 1100% excess of SF 4 . In addition,a 17.5% yield of 3-trifluoromethyl phenanthrene-6-carbonyl fluoride and2.4% yield of 3,6-phenanthrene dicarbonyl fluoride was obtained. Asimilar reaction performed at a lower temperature gave a lower conversion(8.1%) to 3,6-bis(trifluoronethyl)phenanthrene but a higher yield of theintermediates (48% 3-trifluoromethyl phenanthrene-6-carbonyl fluorideand 26% 3,6-phenanthrene dicarbonyl fluoride). This yield data is basedon an analysis of the crude reaction mixture by quantitative GLC and TLCanalysis. These analytical tools were developed during the course ofthis study and can be now routinely used for analysis of 3,6-bis(tri-I±luororethyl)phenanthrcne directly. The major intermediates (3-tri-fluoromethyl phenarthrene-6,-carbonyl fluoride and 3,6-phenanthrene di-carbonyl fluoride) can be quantitatively determined by reacting the crudereaction mixture with methanol and determining their corncentrations basedon the response of the corresponding methyl esters. A purified sampleof 3,6tobist,.rifluorormet.hvl)phtnanthrene was not obtained from these re-actions ýlut studies on the soxhlet extractors showed promise that sep-aration aid l;o•&•ion is possible.

A sample of nurin ied 3,6-bis (trifluoroniethyl)phenanthrene was obtainedby decarboxYlat ing the 3,6-bis(trifluoromethyl)nhenanthrene-9-carboxylicacid. Tdentification of this compound. (section V-A) was confirmed by IR,melting ,oint, NMR, IN and elemental analysic. This sampnle servcd as astandard !','r IT(' ,t:i_ TI,C atnalysis of the crude reaction product.

Corrosion ditti ithered durir.g the course of the p.toluic acid reactions-zhowed a ccrrorion r'ite of (0.002 inches per year on 316 stainless steelunder reatction -onditions.

Continuation of Document Control Data - R&D(Second Page)

An economic evaluation of the production of 3,6-bis(trifluoromethyl)phenanthrere based on a 20% conversion to 3,6-bi6(trifluoromethyl)phenanthrene plus an additional 30% yield of recycleable intermediatesshowed that a selling price (excluding 3,6-phenanthrene dicarboxylicacid costs) of "$15/pound could be achieved at 30,000 to 50,000 lbsper year 3,6-bis(trifluoromethyl)phenanthrene. For smaller require-ments, ("3,000 lbs/yr), the selling price (excluding 3,6-pheranthrenedicarboxylic acid costs) would be *$40/lb. These figures reflect anexpected SF 4 selling price of $10 per pound at the lower productionrate and $3 per pound at the higher production rate.

97