7/7D-l48 286 RESEARCH IN PHASE TRANSFER CT LYSIS(J) TEXAS A AND

M /iI UNIV COLLEGE STATION DEPT OF CHEMISTRY J H FENDLER

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RESEARCH INI PHASE TRANSFER CATALYSIS 4

00

by Janos H. Fendler, PhD

TEXAS A&M UNIVERSITYDepartment of Chemistry

College Station. Texas

DTIC

.:

August 1984

US Army Armament, Munitions & Chemical CommandAberdeen Proving Ground, Maryland 21010-5423

tDST41?UT'~; vw:'84 11 26 083

A. • ., ,.

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V:ELD 770-1P I WL3-CfCUPJ Hydrolysis Catalysis15 02Phase transfer

_______ I -Tol uenesul fonyl fluoride*19. A3STkACr (Continue uts rivo if necessary and .dentity by block number)

I Mechanisms for the hydrolysis of paratoluenesulfonyl fluoride (pTSF) in the aqueoussodium hydroxide cyclohexane two-phase system have been elucidated for differentphase transfer catalysts. The mechanism for the hydrolysis is composite; it involvesboth interfacial and phase transfer catalysis. Experimental conditions determine themechanism(s) which prevails.

h20 01STFiJUT C% AVA.J.,PIUV? OF AiISTRACTV 21. ABSTRACT SECURITY CLASSIFICATIONUNCt.SS E0'1,.V~. ri SA. A5~ QO.[:TIC USR UNCLASSIFIED

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00 FORM 14 73,84 MAR 83 A~PR ectorimay be used untiletausteo. SECURITY CLASSIFICATION OF THIS PAGEAll other editions are obsolete. 'UNCLASS IFI ED

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PREFACE

This research was authorized by Contract No.DAAKl1-79-C-0111, titled "Research on Phase Transfer Catalysis,"with the Chemical Systems Laboratory, ARRADCOM,* sponsoredthrough the US Army Research Office. The work was started inDecember 1979 and completed in December 1980.

The use of trade names in this report does not con-stitute an official endorsement or approval of the use of suchcommercial hardware or software. This report may not be citedfor purposes of advertisement.

Reproduction of this document in whole or in part isprohibited except with permission of the Commander, ChemicalResearch and Development Center, ATTN: DRSMC-CLJ-IR (A),Aberdeen Proving Ground, Maryland 21010-5423. However, theDefense Technical Information Center and the National TechnicalInformation Service are authorized to reproduce the documentfor United States Government purposes.

Access3ion

DTTC .

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*Now the Chemical Research and Development Center, US Army

Armament, Munitions and Chemical Command.

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CONTENTS

Page

1. INTRODUCTION ......................... . ......... 7

2. OBJECTIVES .............................. 8

3. EXPERIMENTAL .............. ............. ......... 83.1 Preparation of Tetra-n-butyl-phosphonium

Hydroxide (Bu 4POH)........................... 8

3.2 Synthesis of -14C Bu 4 PBr................... 8

3.3 Distribution Coefficients ofQuaternary Ions ................................ 9

3.4 Kinetics of Hydrolysis of ParatoluenesulfonylFluoride ....................................... 9

4. RESULTS AND DISCUSSION .......................... 94.1 Hydrolysis of p-Toluenesulfonyl Fluoride ....... 94.2 Synthesis of Tris-butyl 4-Hydroxybutyl-

phosphonium Chloride ........................... 12

5. MECHANISTIC INVESTIGATIONS ................... 12

5.1 Effect of Catalyst Concentration ............... 135.2 Distribution of Water, Catalysts and Products

Between the Aqueous and Organic Phases ......... 135.3 Effect of Changes in the Volume Ratios of

Water to Cyclohexane ........................... 13

5.4 Partitioning of the p-ToluenesulfonylFluoride, pTSF ........... I ....... .... 0 ...... . 14

KL6. CONCLUSION ......................... *.............. 14

LITERATURE CITED ..................... * ........... 15

APPENDIX ......................... ............... 17

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RESEARCH IN PHASE TRANSFER CATALYSIS

1. INTRODUCTION

Advantages of microheterogeneous sy _:tems for tuedetoxification of arylsulfonyl halides became evident recentl>to the Chemical Systems Laboratory*. Microheterogeneoussystems are capable of solubilizing and localizing suchmaterials and providing media for their catalytic degradation.Research had shown that aqueous nucleophilic and functionalmicelles, microemulsions, and polyelectrolytes were powerfulmedia for the destruction of selected arylsulfonyl halides.An alternative approach is provided by phase transfer catalyticsystems.

Phase transfer catalysis is an extremely useful andversatile synthesis technique. -6 Its relative simplicity,speed, and economy have rendered this method invaluable forlarge scale industrial processes. Indeed, new syntheses andgross improvements of existing ones have mushroomed. To date,more than 2000 papers have been published on phase transfercatalysis. Only a handful of these are concerned, however,with mechanistic aspects.

7 - 1 3

The phase transfer mechanism, proposed initially byStarks for nucleophilic substitution,7 involves the transferof the nucleophile, -, from water to the organic phase wheresubstitution on RX occurs. The leaving group, X-, is sub-sequently transported back to water. Transport of the anionsis accomplished by an organic soluble phase transfer agent,typically a quaternary ammonium or phosphonium halide, Q+Y-:

RX + Q+Y- No RY + Q+X-

organic phaseV -(1)

water

Na+Y - + Q+X- Na+X - + Q+Y-

There are two basic tenets of the proposed mechanism. Firstly,the reaction is assumed to take place in the organic phase,rather than in water or at the interface of two immisciblesolvents. Secondly, formation of both aqueous and reversedmicelles is precluded. The observed kinetic behavior ofnucleophilic substitions under phase transfer conditions con-stituted evidence for mechanism 1. Specifically, rate constants

*Now the Chemical Research and Development Center, US Army

Armament, Munitions and Chemical Command.

7

were found to (a) increase linearly with increasing cai.aly:.concentrations, (b) increase with the ability of the catal y-,tto extract the anion into the organic phase, and (c) re'Lm:i.irtinvariant of the stirring rate (beyond 300 rpm). Kineticschemes have recently been derived for ph:-se transfer catalyse.scharacterized by mechanisms analogous to that given inequation 1.5,10 These derivations implicitly assume that thetransfer of the reagent from the aqueous to the organic plo:-eis fast compared to the substitution. Reactions other thannucleophilic substitutions may well be governed by rate-limiting transfer of the reagent across the boundary separatingthe phases. Indeed, acceptance of riechrtnisri 1 for .l1 r-actions occurring in two-phase immiscible systems is notwarranted. Conceivably, reaction sites may involve thepolar-apolar solvent interface.

2. OBJECTIVES

The objective of this research has been to examinethe feasibility of phase transfer catalysis as a viablehydrolytic method. Rates and mechanistms for the destructionof paratoluenesulfonyl fluoride have been determined underphase transfer catalytic conditions.

3. EXPERIMENTAL

3.1 Preparation of Tetra-n-butyl-phosphonium

Hydroxide (BuaPOH1)

Tetra-n-butyl-phosphonium bromide (Bu 4 PBr), Aldrich,was recrystallized from ethyl acetate. Ten milliliters of' 10 Maqueous Bu 4 PBr was shaken 30 minutes with 3.0 gm of AG2 0 andcentrifuged. A bromide ion selective electrode was used todetermine the extent of the reaction. No bromide ion could be, detected after completion of the exchange.

* 3.2 Synthesis of [1- 1 4 C] BuaPBr

* 1- 1 4C-labelled Bu 4 PBr was made by refluxing 0.010,-. moles of tri-n-butyl-phosphine with 0.10 moles of [I- 1 4 C]n-butyl bromide (specific activity = 3.87 mCi /mmol) in 2 mlof absolute ethanol in a sealed ampoule at 85 C for 160 hours.The reaction was stopped by cooling the ampoule with liquidnitrogen. After distilling off the solvent, a saturatedsolution of Bu 4PBr in 10 ml of hot ethyl acetate was pouredinto the ampoule. The crystallized product was washed withcool ethyl acetate and dried under vacuum overnight. Theresulting product had a specific activity of 0.81 mCi/mole(yield = 10%).

8

p.'7"

3.3 Distribution Coefficients of Quaternary Ions.

Base concentrations in the organic phase were determinedas described by Herriott and Picker.8 Distribution coefficientsof Bu 4 P+ ion and H2 0 between water and cyclohexane were determinedusing 1-1 4 C Bu4 POH or bromide (.817 mCi/mol) and 3H 1120 (0.074

- mCi/Mol). Radioactivities were counted on a Beckman SLlO0scintillation counter using a 1 3 7 CS external standard to correctfor quenching.

3.4 Kinetics of Hydrolysis of Paratoluenesulfonyl Floride(-TSF).

Kinetics runs were carried out in a 100-ml two-neckedflask fitted with a stirring motor. The stirring speed wasdetermined with a stroboscopic tachometer at least three 4 ;s

during the kinetic run. The reaction vessel was immersec' A aconstant temperature bath. The temperature inside the fl-skwas maintained at 25.00 + 0.5°C. Usually 15 ml of cyclohe-phase was stirred with 50 ml of a 4 M NaOH water solution ot the

- catalyst. The reaction was stopped by pouring out an aliquot ofcyclohexane phase over spectranalyzed grade cyclohexane to theproper dilution. Concentrations of pTSF were determinedspectrophotometrically at 267 nm using a Cary 118C spectrophotometer.

4. RESULTS AND DISCUSSION

4.1 Hydrolysis of p-Toluenesulfonyl Fluoride.

Rate constants for the hydrolysis of p-toluenesulfonylfluoride have been redetermined in the phase transfer systemusing tetrabutylphosphonium bromide (Bu 4 PBr) as catalyst.Particular emphasis has been Placed on determining the concentrationof the hydroxide ion in the organic phase and examining the effectsof an added electrolyte on the hydrolysis rate. The results are

- * contained in Table 1. It is seen that sodium chloride does notappreciably alter the rate of hydrolysis in the absence ofcatalyst. This result obviates the need for investigating theinfluence of electrolytes on partitioning p-toluenesulfonyl fluoridebetween water and cyclohexane. Rate constants for the hydrolysis ofp-toluenesulfonyl fluoride in the phase transfer system in thepresence of increasing amounts of Bu 4 PBr are given in Tables 2 and3. Rate constants in all cases had been followed to 99.5% com-pletion of the reaction. The agreement is good between rate con-stants determined in the cyclohexane and in the aqueous phases, andthe correlation coefficients are excellent. The catalyticefficiency of the transfer agent is impressive. Rate enhance-ment as a function of added catalyst is linear (see Figure A-I),

* but, as a function of OH- concentration in the cyclohexane phase,.:the rate increase is shown to be exponential (see Figure A-2).

90

2;-

'fable 1. Hydrolysis of p-Toluensulfonyl Fluorido*in H20-Cyclohexane in the Absence of Phase

Transfer Catalyst at 25.COC

* -[NaOH] , NM 1o5[OHrj, M 10 3 k se 1 1 3k~

- .in H20 in cyclohexane in cyclohexane rin H0

1.0 4.0 3.1 .9996 2.66 .99962.0 6.0 3.6 .9989 3.1 .99.3.01 6.0 1.71 9981.6

3.82 8.0 1.63 .9968 1.32.0 + 2.15 .99852. OMNaCl

*Determined spectrophotometrically. All rates were followed to 99.9,1)completions.

Table 2. Hydrolysis of p-Toluenesulfonyl Fluoride*

in H20-Cyclohexane in the Presence of PhaseTransfer Catalyst at 25.000

103 [Bu 4PBr] , M 104 [OH-] , M 103k, , sec-1 r 03k*, sec-in H20 in cyclohexane in cyclohexane in H120

0.0 0.80 1.63 .9968 1.30 .9980-. 6.5 2.90 .9965 2.90 .9-.-

7.5 2.82 .9991 2.67 .999510.0 5.0 4.50 .9980 3.67 9 93 812.0 3.10 .9960 3.00 .998220.0 14.0 4.20 .9960 2.90 .9913

*30.0 21.5 8.07 .9117 2.58 .990440.0 24.5 10.80 .9740 6.50 .9927

*50.0 17.0 17.50 .9804 19.80 .9180100.0 32.0 41.20 .9980

*Determined spectrophotometrically. All rates were followed to 99.95%comple tion

* 10

* - Table 3. Hydrolysis of p-Toluenesulfon ! Fluoride*in the Presence of Different Types of iatalysts

Cataystin cyclohexane in cyclohexane

10 mm (Bu4P)2S04 1.7 4.8[0 mM Bu4 PBr 2.9 5.0Uncatalyzed 1.6 0.810 Mnv Bu3PBuOHCl 2.3 1.4

10m uPOH 3.44 34.350 mM Bu4POH 36.75 39.050 mM Bu4 PBr 27.0 17.5

* *Determined spectrophotometrically. All rates were followed to99.95% completion.

T.. -77

1.2 Synthesis of Tris-butyl-(4-hydroxybutyl )phoshoniuixi~Ch I or i de.

A phase transfer agent capable of forming an in-ternal ion pair with hydroxide ion may be a more efficiontcatalyst than Bu 4 P+Br. With this in mind, tris-butyl-(4-hydroxybutyl)phosphonium chloride was synthesized. The r(action was started by addition of an ethanolic solution of 4-chlorobutanol to tributylphosphine. After four days, the re-action was shown to be complete by means of a chloride ionselective electrode using a potentiometer. Stirring was c,-t inued for an additional day to ensure that there was no0"aturation effect of the product, phosphonium chloride (seuFi-ure A-3). The solvents and reagents were then ovaporuitedunder vacuum (1 mm Htg at 170'C, the boiling point of Bi'*).The remaining solid was dissolved in water and then extractedwith ethyl ether. Long plates crystallized from the etherextract after one week. The water extract did riot crystallize,but both products showed the same NMR and If? spectrum. NMRspectrum: -Ct3 , 9H, 3.3 ppm; -CH 2-, 26 11, 1.6 ppm; -0I, li,

* 1.0 ppm. The observed ratio of -011 to -C'13 , plus -C12-1:35.22.) IR spectrum: S 3.4 p, 3.5 p; W 4.05 ji; W 6.1 pi;\1 7.1, 7.25, 7.45, 7.7 ji; S 8.2, 8.7 i N1 9.2, 9.5, 10.0, 10.3,11 ji; S 13.2 p. The alcohol signal was identified by driiviltza-tion with acetic anhydride or trifluoracetic acid; Off hands at3100-3 300 cm - 1 disappeared.

Rate constants for the hydrolysis of p-toluenesul tonylfluoride were determined by titrating the cyclohexane phase a.sa function of time, as described by Hlerriott and Picker.

8

Bu 3 (J10Bu)PCT appeared to be a much better catalyst than Bu 4 1110.

MECHANISTIC INVESTIGATIONS

Figure A-4 shows the effect of changes in concentra-tion of tetrabutylphosphonium hydroxide (Bu4 POI) and changes instirring speed upon the pseudo-first-order hydrolysis rateconstants for paratoluenesulfonyl fluoride (pTSF) in the twocomponent aqueous 4 M NaOll system. The rate is seen to in-crease with increasing stirring speeds at all catalyst con-

centrations. At the lowest catalyst concentration (30 mM)there is a hint of leveling off. Clearly rates do not leveloff at concentrations of 40 mM and 50mM Bu4 POIl. Figure A-5compares the catalytic efficiencies of Bu 4POHl and tetrabutyl-pho phonium bromide, Bu 4PBr, as a function of stirring speed.Althouh the extractability of Br- is several hundredfold

greater than Oil-, appearance of a third oily phase in thepresence of Bu 4 PBr is at least partially responsible for thepoorer performance of this catalyst. The solid thick line in-igure A-5 shows the effect of stirring speed on the rates for. nuclceophilic substitution under true phase transfer conditions.

-2

The mechanism for the hydrolysis of pTSF in the present aqueous4 N NaOl-cyclohexane two-phase system is clearly different fromthat described by pure phase transfer catalysis. Coexistence ofinterfacial and phase transfer catalysis is more probable although aphase transfer mechanism prevails to a greater extent forBu 4 PBr than for Bu 4POH. Under our experimental conditions,most of the Bu 4 POH catalyzed hydrolysis of pTSF appeared tooccur at the water-cyclohexane interface.

5.1 Effect of Catalyst Concentration.

. Concentrations of Bu 4PBr and Bu 4 POH in the organicphase were measured by a bromide selective electrode and bytitration, respectively. The observed rate for the hydrolysisof pTSF increase exponentially with increasing catalyst con-centrations at all stirring speeds as indicated in Figures A-6and A-7. At very low stirring speeds, the kinetics followedzero-order rate laws which became pseudo-first order atstirring speeds greater than 350 rpm. Similarly, in thepresence of catalyst concentrations above at 0.03 M, theobserved kinetics are pseudo-first order at any stirringspeed. We interpret this behavior to be a change of mechanismfroma rate determining transport of the reagent to ratedetermining hydrolysis.

5.2 Distribution of Water, Catalysts, and ProductsBetween the Aqueous and Organic Phases.

The catalyst and water concentrations in the organicphase as a function of separation time following centrifuga-tion are shown in Figure A-8. Interestingly, the catalystconcentration in the organic phase is independent of thenature of the counter ion. Importantly, the distributionof both the catalyst and water decrease exponentially to alow level as a function of phase separation time. Con-centrations of water and catalyst are, therefore, extremelyhigh during the reaction at the interface. Paratoluenesulfonicacid, the product of the hydrolysis of the fluoride, issoluble in cyclohexane. Unlike Starks and Liotta, we didnot find the hydrolysis to be inhibited by added para-

* toluenesulfonic acid. This is not compatible with the notionthat phosphonium salts act only as phase transfer agents.

5.3 Effect of Changes in the Volume Ratios of Waterto Cyclohexane.

"0 Changes of the ratios of water to cyclohexane dramat-ically affect the rate of hydrolysis (Figure A-9). Increasing

* . -- the volume ratio of water to cyclohexane increases the ratetwelvefold. Increasing the volumes of both phases also

13

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~~~~~~~~~~.....:.'.....'.... ........ ..... : .. ;................

increase,, the hydrolysis rate. These observations can berationalized in terms of creating larger interfacial areasfor the hydrolysis by increasing volumes, increasing stirringspeed, and increasing ratios of water.

, 5.4 Partitioning of the p-ToluenesulfonyI Fluorbt_ prTSF.

Using the standard U-tube with cyclohexane in the twoarms, we studied the transport of pTSF from one side of the U-tube across an aqueous solution containing NaOlt and BuIPOHi.

The kinetics of transport appeared to follow thezero-order rate law. This result substantiates our postulatethat, in the presence of catalysts and at appropriate stirringspeed, transport of the reagents across the interface is last

*compared to the rate of hydrolysis.

6. CONCLUSION

Studies under this contract have demonstrated theutility of phase transfer catalysis for the hydrolysis of

, paratoluenesulfonyl fluoride. Substantial enhancements ofthe hydrolysis rates have been elicited. The mechanism forthe hydrolysis appears to involve both interfacial and phasetransfer catalyses. Experimental conditions determined theprevailing mechanism.

Based on these studies, further investigations in. order to optimize phase transfer catalysis, as well as for

critical comparison of this method with others available, arerecommended.

14

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LITERATURE CITED

1. Brandstron, A. Adv. Phys. Org. Chem. 15, 267

(1977).

2. Makosza, MI. Russ. Chem. Rev. 46, 1151 (1977).

3. Weber, W. P. and Gokel, G. W. Phase-Transfer('at alysi.s in Organic Synthesis. Springer-Verlag, Berlin.

* 1977.'

4. Dehmlow, E. V., and Dehmlow, S. S. Phase* Transfer Catalysis. Verlag Chemie, Weinheim and New York.

* 1978.

5. Starks, C. M., and Liotta, C. Phase TransfurCatalysis. Academic Press, New York. 1978.

6. Keller, W. E. Compendium of Phase-TransferReactions and Related Synthetic Methods. Fluka AG, C11-947(,

* LBuchs, Switzerland. 1979.

7. Starks, C. M., and Owens, R. At. J. Am. Chem.Soc. 95, 3613 (1973).

8. Herriott, A. W., and Picker, D. J. Am. Chen.Soc. 97, 2345 (1975).

9. Freedman, H. H., and Dubois, R. A. Tetra-

hedron Let. 3251 (1975).

Soc. 10. Gordon, J. E., and Kutina, R. E. J. Am. Chem.So.99, 3903 (1977).

11. Landini, D., Maia, A. M., and Montanani, F.Chem. Comm., 950 (1975).

12. Landini, D., Mfaia, A. M., and Montanari, F.J. Chem. Soc. Chemn. Comm., 112 (1977).

13. Landini, D., Maia, A. M., and Montanani, F.J. Am. (Them. Soc. 100, 2796 (1978).

15

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APPENDIX

FIGURES

40

30

02

120

H CYCLOHEXANE PHASE

0 WATER PHASE

50 100

CONC OF Bu4PBr, MM IN WATER

Figure A-1. Effect of Catalyst on Hydrolysis of PTSF

17

100-

'.10-

10 10

-44

CONC 01 01-1- IN CYCLOHEXANE 10 iM

Figure A-2. Effect of Concentration of Hydroxyl ionin Cyclohexane Phase on Hydrolysis of PTSF

App ndi.1

IN.

150-

E

U 100-U.

'p. 0

'p. z0 .0c-

Z 50-

780C

I I

EtOH

100-

01 2 345 6 7 8910TIME, DAYS

*g

* Figure A-3. Formation of Tributyl 4-hydroxybutylphosphonium Chloride

: Appendix 19

* -. 4-... 4 0 135

-*4'-... * *%TIME, DAY

* 77

BU4 POH 50mM90- 91.55 ±00.65

80-

70-

60-

* ~50-

E40~~ B.U4 rPjr 4umMv

30-

20 /,0 BU4 POH 30mM

10 -

WITHOUT CATALYST0-

*0 1000 2000 3000 4000 5000RATE OF STIRRING, RPM

Figure A-4. Effect of Rate of Sti rring onHydrolysis of PTSF Using Bu P OH

A4

Appendix

20

ABU4POH 50mM.490- A

80-

- - 70 -

60-

o50-

CAA

S TRUE PHASE TRANSFER CATALYSIS

30 - .u Bu4 PBr 50mM

20

01

1000 2000 3000 4000 5000 6000

* RATE OF STIRRING, RPM

Figure A-5. Effect of Rate of Stirring onHydrolysis of PTSF, Using Bu POH and Bu PBr

Appendix 21

-~ ~ %

200 £EXTR.2760 RPM

150

0 100

0V 100 RP

50

#1000 RPM

10

0 10 20 30 40 50 60 70SBU 4PBr, mM IN WATER PHASE

Figure A-6. Effect of Cencentration of Catalyst in WaterPhase and Rate of Stirring Upon the Hydrolysis of PTSF

Appendix 22

~i4.--4 " - . 4 .. ****4 -

4'".4-.*7*.. - *44 --- * -. ~ *

2750 ±20 RPM

200-

150-

*U

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50-

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0 10 20 30 40 50 60 70 80 90 100BU4 POH, mM IN WATER PHASE

Figure A-7. Effect of Concentration of Catalystin Water Phase on Hydrolysis of PTSF

Appendix 23

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CETRFUATO TIE IUE

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130-

120 '110 I

100 I

90 I

80-

~" 70 g

60-

50 50

4 0 - I

30 -1000 RPM

20- If Bu4 POH 50mM

10 / A 1760 RPMBU4 PBr 50 mM

r -- T- T I I I

0 10 20 30 4050 6070 80 90100

VOLUME PERCENT, WATER PHASE

Figure A-9. Effect of Ratio of Water toCyclohexane Phase on Hydrolysis of PTSF

Appendix 2

-7

*FILMED

1-85

DTIC