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AD-787 278

CHARACTERIZATION OF SELECTED TR I ARYLMETHANE LEUCONITR ILES

M. L. Herz

Army Natick Laboratories Natick, Massachusetts

March 1973

DISTRIBUTED BY:

National Technical Information Service U. S. DEPARTMENT OF COMMERCE

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X,' FOREWORD

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The iTitryimrthmn» leuconitriles are of considerable interest in the field of eye protectior, end infonaetion on their fundamental characteristic!» ie not available. These date from spectroscopic studies of these compounds provide a basis for measurement of their basic photo- chemical properties.

The work was carried out in the Flame amd Thermal Protection Section of the Chemie«! Modification of Textiles Branch of the Textile Research and Engineering Division under Materials for Flashblindness Protection, Pro- ject IT062I05A349„ Tesk 05.

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TABLE OF CONTENTS

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a

FOREWORD

I. INTRODUCTION

II. OBJECTIVE

III. DISCUSSION

IV. EXPERIMENTAL SECTION

A. Materials and Instrumentation

B. Preparation of Doebner's Violet Leuconitrile

C. General Procedure for Leuconitrile Preparation

V. SUMMARY

VI. REFERENCES

VII. APPENDICES

APPENDIX A - List of Tables

1. Details of Preparative Procedures for Leuconitriles

2. Physical Properties of Triphenylroethane Derivatives

3. Ultraviolet Spectra

APPENDIX B - Mass Spectral Data

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I. INTRODUCTION

The use of photochromic compounds in optical (eye protective) devices has been under consideration for some time. (1,2,3,4) Construction of such a device, utilizing solutions of spiropyrans in filter cells surrounded by flash- tubes, has demonstrated the feasibility of this approach. The development of an optical device with satisfactory fundamental, bilk, and weight characteris- tics would require a significant improvement in speed of response, optical density, *?* non-fatiguing (recycling) properties.

As a class, the triphenylmethanes exhibit a higher extinction, cc—efficient and permit greater control of return rate than the spiropyrans.'•' The color- lass leucocyanides of the triarylroethanes are converted by intense light to the highly-absorbing colored form. To furnish information essential to the develop- ment of a useable eye protective system, the characteristics of a series of systematically substituted triarylmethanes were measured.

Although some melting points and electronic spectra have been published for several of the leuconitriles of interest, a complete study of the properties of a series of these compounds was needed to permit elucidation of the mechan- isms of color change and fatigue, and thereby provide a basis for improving the photo;hromic response and reducing side reactions.

II. OBJECTIVE

The objective of the present phase of the work with triarylmethanes was to synthesize and characterize completely (using uv, ir, nmr and mass spectral techniques) the leucocyanides of six triarylmethane dyes and one related model compound, triphenylacetonitrile.

III. DISCUSSION

Of the six di- and triamino substituted triarylmethane dyes needed for syn- thesis of the series of leucocyanides Qa through 3b), all but one were available.

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For Doebner's Violet (4,4'- diaminotriphenylmethyl cation), it was necessary to devise a satisfactory synthetic path. (The procedure described in the literature gave extremely poor yields, it is probable that nona of the pure product was actually isolated). Neither the leuco- nitriles of Doebner's Violet (la) nor of Turquoise Blue (3b) had pre- viously been reported.

The general procedure followed for the synthesis of all the leuco- nitriles is given here in detail (4£) along with a tabulation of the specific conditions found best for each dye (Table I).

The complete characterization of the six leuconitriles was carried out. The resulting data, obtained by ir, nmr, uv, and mass spectral tech- niques, are given in Tables II and III. For those melting points and uv spectral characteristics which have been previously published^references to the original data are given.

IV. EXPERIMENTAL SECTION

A. Materials and Instrumentation

All melting points were measured on a Thomas-Hoove* melting point apparatus and are uncorrected. Ir spectra were determined in potassium bromide on a Perkin-Elmer Model 521 spectrometer. Nmr spectra were recorded

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on either a Varlsn A-60 or HA-ICX) spectrometer with an internal tetramethyl- silane standard. All the ultraviolet spectra wer* measured on a Cary 17 spectrometer in spectral grade solvents as Indicated. A Ferkin-Elmer Model 270 or a Consolidated Model. 21-110 mass spectrometer was used. Ele- mental micro-analyses were performed by Midwest MicroLab, Ltd.

The following reagent grade dyes were used in the preparation of the leuconitriles: Crystal Violet, Pararosaniline Base (j. T. Baker Chemi- cal Co.), Malachite Green (Matheson Co.), Turquoise Blue G (Verona Dye- stuffs), and Brilliant Blue or Rhoduline Blue (GAP Corp.).

B. Preparation of Doebner's Violet Leuconitrile

1. k,k' - Diaminotrlphepyimethane^)

The procedure of Baeyer and Villiger (°) was followed. In a 1-1 three necked flask equipped with a condenser, mechanical stlrrer, and glass stopper, were placed 76 sei (80 g, O.76 mol) of benzaldehyde, 80 g (0.62 mol) of aniline hydrochloride, and 313 ml (320 g, 3.W* aol) of aniline. The solution was heated with stirring until it began to reflux (l hr.). At this point the solution was allowed to cool. It was then made basin by the addition of 50 mi of a 60$ sodium hydroxide solution. The resulting mass was extracted three times with 200 ml portions of hot acetone. The acetone solution was evaporated to a smaller volume (ca. 150 ml) and l',0 ml of ben- zene was added. This solution was heated, decolorized with charcoal, fil- tered and dried over magnesium suifate. Upon further reduction in volume, a solution was obtained which produced crystals when cooled.

I I

A solution in benzene (120 ml/g) of the solid product was reduced to one half its original volume, yielding J+ (15^-7 g, O.56I. sol, 7ty): mp 107-09° (lit. 8 mp IO5-O60) after four recrystalli- zations from beuzene: ir 3kkO, 336o(H-H), 306O, 3020 (unsat. C-H), 2920. 2860, (aliphatic C-H). 12Ö0 (C-H), 820 (p-aromatic). 750 and 700 cm"1

(monoaromatic), nmr (cOCLj), 87.16 (s,5), 6.88 (m,8), 5.32 (a,l,CH) and 3.1+L ppm (s,2,RH2)*

The diacetate of U,U' - diaminotriphenylmethane '5) was prepared in essentially 100> yield by treatmeot of k (150 g, O.577 mol) with 150 ml (162 g, 159 mol) of acetic anhydride In >0 ml of glacial acetic acid (EXOTHERMIC). After one-half hour, the solvent was removed in a rotary evaporator. The product crystallised Irom methanol to give the desired product: mp 236-37° (Lit. ° mp 233-35°).: ir 3300, 3190, 3120 3050 (broad), 2920,2860, I665, 1600, 1550, 1320, 810, 7to, 720, and 700 cm"1.

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2. Attwupto d Oxidative Synth—■ of Doobair's Violet

a. Oxidation with MmMMM Dioxide

The reaction was carried out in a 300-al Erlenmeyer fU*k with magnetic stirring. To a mixture of 5 g (0.014 mol) of £ in 60 al acotlc tel^t 9 al sulfurlc acid and 17 al of water„ 0.610 g (0.007 mol) at manganese dioxide (in another run»twice tbi» «muunt of dioxide wee used) were added with stirring and cooling in a water bath. The mixture was stirred vigorously for 36 hr end then tieated with 23 g (0.3 mol) of potassium hy- droxide in 25 ml of water. The materiel «soleted after washing was un- changed starting material (^4.9 g; mp 236-37°).

b. Oxidation with Pota»slum Permanganate

To a solution of £ in acid solution, as above, 0.865 g (0.0055 aol) of potassium permanganate in 20 ml of witter were added at such a rate that the solution temperature wes kept1 at cjf. 10°. The solution wes stirred for 15 additional minuteo, 5 ml of ethenol added and finally 20 g .(0.5 mol) of sodium hydroxide. The precipitate which formed wes filtered and washed. It wes identified as starting materiel (4.3 g; correct lr and op).

This reaction was also attempted with three times the calculated amount of permanganate. In this run, the reaction mixture was slowly heated to reflux temperature. Again, only starting material could be re- covered .

c. Oxidation with N-Bromsucclnlmld« CMS) (9)

(1) Attempted Oxidation of Placetvl-4.4*-dlamlnotrl- pheoTlmethane (5)

Compound ,£ (5.0 g, 0.014 mol), 1.8 g (0.0107 mol) of UBS and 40 ml of carbon tetrechlorlde were mixed In a 100 ml round bottom flask equipped with reflux condenser. The mixture was r«fluxed In an oil bath for 32 hr. The starting materiel wes recovered unchanged.

(2) Attempted Oxidation of Placetvl-4.4'-diemin0l:rl. phenvlmstbene (4)

G«apound J^ wau treated in the manner described above for compound £. The solvtmt wes removed by evaporation, leaving a reddish tar. Infrared analysis showed the ter to contain e mixture of the reectents; none of the desired product coe'd be Identified.

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Tn a U T; rJtjtrA bottoa flask the ifi-p-animotri- pheny)«ethane (3.0 g, 0,011 mol) »na Ki-S (*.Ö g, 0.0101 mol) in chloroform (50 ml) were refluxed for 6 hr under a lOC-v&it xenon mercury source. The email amount of precipitate which formed and remained after washing (3X) with carbon tetrachloride was composed (tic on silica) mainly of NBS, probably some DV (small purple spot), a trace of k, and unidentified resinous materials.

(k) Attempted Oxidation of h,k' - Diaminotrlphenylmethane Catalysed by Irradiation and Benzoyl Peroxide

Tbe triphenylmethane k was tr»:^^d in chloroform solu- tions as above with G.3 g (0.00123 aol* 10 mol %) benznyl peroxide and HBS at reflux under Irradiation for 20 hr. An additional 10 mol $ of benzoyl peroxide was added and reflux continued tor two more hr. The solvent was removed by evaporation and the solid remaining analyzed by tic. Only trace amounts of the desired product could be detected.

3. ktk'-Diaminotriphenylmethane

In a 100-ml reaction kettle equipped with an air condenser, 5.0g (0.01Ö mol) of U,lf'-diaminotriphenylmethanol (k), U.50 g (0.01c& mol) of Q chloranil and kO ml of eblorobensene were heated with magnetic stirring at ca. 67 . After five hours the solution was» allowed to cool and the insoluble products were separated by suction filtration. This crude uroduct (5*5? g) vas finely ground with a mortar and pestle, then extracted continuously with benzene in a Soxhlet extractor (W hr) until essentially one spot was found with the tic on silica gel (developed with 10$ methanol in methylene chloride). This product was chromatographed on a silicic acid column (lOO mesh). Elution with chloroform yielded tetrachlorohydro- quinone (0.3te g, mp 233-35°C); with ether and 5$ methanol in methylene chloride, untractable oils (successively yellow and green); and with increasingly polar 10- 20$ methanol in methylene chloride, Doebner's Violet, (3A5 g, 65.5$). The last material waa a green powder which did not melt at temperatures below 350°C; however, it appeared to be a single compound from the tic (M-H), 3120. I63O, 1610. 1580, IHUO, 1270, 1335, 1 dg ) 8.40 (broad a, 2, fagV* f»06 (m, 13, aromatic Upon deuterium exchange the peaks at Ö.kO and 3*^9 ppm attributable to the ammonium aci amino groups, respectively disappeared leaving the aromatic multiplet essential- ly unchanged.

To obtain very pure dye the material wa3 chromatographed in the above manner twice. This insured the high purity (by tic) of the dye which was necessary for the sue 3 of the conversion to leuconitrile.

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A solution of 5.82 g (2,00 tamol) of Doebner's Violet (6) in ISO ml of methanol was hMtad on a staaa bath and treated with 2.0 g (4.08 mmol) of sodium cyanide to produce a green colored mi -tur«. The mixture was auction filtered, the filtrate evaporated to drynesa on a rotary evaporator, and the reaidue extracted repeatedly (5X «1th 60 ml portion«) with hot bensene. The bensene was decolorlied with charcoal and reduced in volume to 100 ml to give crystals. These, upon recryetallliatlon from bensene and athanol containing a trace of sodium cyanide, gave £a (4.35 g, 1.45 mmol, 72.5Z)t mp 225-26*; ir, 3480, 3390 (N-H), 3060, 2240 (C ■ N), 1630, 1610, 1530, 1447, 1435, 1300, 1185, 830, 766, 705 cm-1; nmr (DMSO-dg)^ 7,2 (m,J#, aromatic),, 6.65 (quartet, 8, aromatic), 5.22 and 4189 pom (2, NH-); aess spectrum (70 eV) m/S (relative Intensity) 299 (71.9, Mf)B 223 (30.5), 222 (100), 207 (29.8), 195 (12.0), 190 (10.3), 182 (3.2), 150 (120), 28 (68.5).

C Oenerel Irocoduro for Leuconltrlle Preoeration

The dye ("Sg) waa dissolved in a minimum amount of dlmethylsulfexlde (shown *n Table I) at ca., 85*. To thla highly co i»red solution sodium cyauide (HOOD!) wan added in small portions until the color of the dye was discharged. Charcoal wee stirred <.nto the hot solution. The mixture »me filtered, the filtrate was heated to ca., 90*, and water was carefully added (See Table I) until the solution began to fog. The material forced out of solution was resolublliied by heer.lng up to ca.. 115*. The solution waa allowed to slowly cool to 0* in order to produce crystals. The crystals were purified by repeated crystallisation from solvents containing a trace of sodium cyanide. Teble I gives the specific conditions and quantities used In the preparation of the various leuconitrHas (lb, 2a-b, and 3a-b).

V, SUMMARY

While many triarylnethane» have been prepared, the yields of these preparations have often been poor. The present, work describes e general procedure for producing these compounds with excellent yields even from relatively impure sterting material.. The utility of tho technique la demons traced by the synthesis of several leuconitrlles.

The comprehensive characterization of theae compounds by spectral techniques gfvee lergely new data which supports the proposed structures, and provider a heals for a study of the chemistry of this class of compounds.

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REFERENCES

1. Fox, R. E., Development of Photoreactlve Material« for Eye Protective Devices. USAF Aeroapaca Medical Center (ATC). April 1961. AD261608

2. Little» Arthur D. Inc., Photochroalc Material» Systems Research, aubcontract to EG&G under Contract No. DA-36-038-AMC-2960 (A) March 1966,

3« Dreyer, J. F., R. W. Harris, R. N. Macnair, And D„ Feldaan, Investigation of Material» and Systems for Protection again«t Flaahbllndnaaa Effect« of Wuclear Detonation» (Phaae I), Contract DA19-129-AMC-112 (N) Polacoat, Inc. Report 68-38-CM, U. S. Any Natlck laboratories, Natick, Maas. Feb. 1968.

4. Bertelson, R. C, at al. Effort to Evolve a Method of Eye Protection frca Flaahbllndneaa. Contract No. AF41(609)-4957, National Caah Register Co., U. S. Arpy Natlck Laboratories, Natlck, Mi»». (1966).

5. Edgerton, Giraeahausen, & Grier, Inc., Development of improved Eye Protective Goggle». Contract N62269-1430, U. S. Aray Natlck LaN>ratoriea, Natlck, Maas. July 1966.

6. National Caah Register Co., Nuclear Antiflaah Shutter System for Teloecope XM-126, Contract DA-36-038-AMC-4368 (W), U. S. Army Natick Laboratories, June 1967.

7. Robinson, I. D. and J. C. Gerlach. Photochromlc Trlaylmethane Solution for Flaahbllndnaaa Protection, Appl. Opt. £, 2285 (1969).

8. VonBaeyer.A. and V. UUllgen, Chea Bar. 3^, 286 (1904).

9. DJeraesl, C. Chea. Rev. 43, 271(1948).

10. Pikl, Joseph, U. S. Patent 3,098,081 (1963), Lewis, E. S., J. M. Perry, and R. H, Grlnsteln, J. Aaer. Chea. Soc. jJ£, 899 (1970) and reference» therein.

11. Herria, L., J. Kamlneky, R. G. Simard. The Absorption Spectrum of MdVuchite Green Leucocyanlde and the Mechanism of the Dark Reaction after Photolysis, J. Aaer. Chea. Soc. j£, 1151 (1935)»

12. Little Arthur D., Research on Photochroalc Compounds for Flashbllndness Protection, subcontract to EG&G under Contract No. N-62269-2717 U. S. Army Natick Laboretorlea, Natlck, Maes. August 1965.

11

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13, Holmes, E, 0. Jr.. The Phototropy of Malachite Green Leucocyanid« in Sthyl Alcohol, Cyclohaxane, Ethylene Dlchlorlde and Ethylidene Dlchlorlde, and Some Mixtures of Them. J. Phys. Chem. 61, 434 (1957).

14c Spores, A. H. PhotoIonisation of Triarylmethyl Leuconitriles, Trans. Faraday Soc. £7, 983 (1961).

15. Calvert, J. C. and H. J. L. Rechen. Precision Actinomatry at Low Light Intsnsifiar with Malachite Green Leucocyanide, J. Aaer. Cham. Soc. 24, 2101 (1952). **

16. Budde, W. M. and S. J. Polempa. The Preparation of Dl- and Triphanylace- tonitrile and Thair Cuprous Halide Complexes, Ibid. 1J^ 258 (1952).

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■Wpi^WW«IWWWI|tJ|^l'^^'WW^WJ)IW*,l>iU-.''^'rr^^' " "■.IM,..».»,.»I» "!■■■■ "",■«' ■ ».■I—■»"-!»" i, .'I'.HKL.'- UM imW&^IW.+*W*~."P***Wm,mfmmMl^t>t**-'l.*f-WWt<*<h-.'*>*-*J*Vl-'L' "T^

APPIRDIX

MASS SPECTRAL DATA

18

' '*lll* :«l ^mm^^tr^mmsrnma« iu m.

r

MASS SPECTRAL DATA FOR TUA1YLM.2HYL LEUCOEITRILKS AMD RELATED SUBSTAHCES. (RELATIVE ABURDAÄCES AS A

PEROEMXAGE OP THE EASE PEAK)

'*« B^riü!™yJÄe*iJC>?±t,r±1** C» «.»-»l^thylMUla«. D, TTiphanylac«-

I» Ehodullna

A, Anilin«. t«#ultrll« _ —... „»W.UUUII rt rararoaaouiaa G, Malachit« Grtan Lauconltrll«. H, Cryatal Violat Lauconitrila Blue LducocJ.tr11«. J, Turquoiaa Blu« Laueonltrll«.

H/«

.

23 0.45 0.88 0.12 A t ■•

26 27 28 29 3D

2.22 3.01 6.99 0.40 0.67

5.69 9.94

62.42 3.07 1.40

1.42 4.43 3.33 0.80 0.61

u 8.0

13.8 7.6

68.5

6.8 12.7

100.0 7.a

1.2 2.3

38.5

0.47 1.36 5.25 4.33 0.86 « «A

1.7 6.0 9.2

1.04 1.92 1.79 2.28

31 32 16

0.34

0.50

5.08 12.66 0.88

0.52 16.98 21.4

5.8 7.7

1.22 0.51 0.88

1.30 2.18

37 4.10 5.87 1.20 38 7.44 9.86 2.95 39 40

17.32 6.04

22.60 4.82 1.25

21.1 6.2 5.74

41 5.96 3.37 2.09 42 43

1.66 .69

1.45 3.07

10.19 1.97

13.4 17.0 8.7 9.79 44 1.84 3.73 29.4 23.8 44.5 1.06 0.88 45 2.80 0.90 45.5 1.97 1.40 46 1.49 46.5 7,02 47 0.51 49 0.81 2.80 0.62 50 4.10 16.21 7.33 3.68 51 4.48 22.43 16.25 4.1 4.9 6.11 4.15 52 5.47 4.56 5.10 3.78 53 1.77 1.50 1.21 54 4.74 55 10.9 4.2 58.5 3.24

19

M/«

60 60.5 61 62 63 64 03 66 67 69 74 75 76 77 78 79 87 88 89 90 91 92 93 94 95 95.5 101 102 103 104 105 106 108 113 114 115 116 117 118

1.81 2.67 4.77 2.87

18.40 33.68 4.62

1.10 0.60 1.25 1.25 1.82

2.19 3.94

0.23 0.97

11.13 100.00

6.99 0.21

4.38 8.59

17.17 6.88 8.32 1.31

3.94 3.29 2.76 9.37 1.71

2.19 3.94

23.16 40.47 22.78 10.42 0.96

2.19 4.65

3.70 2.24 3.49 1.08

2.05 1.61 1.68

24.74 6.18 4.37

0.91 4.55 1.89 1.26 0.82

5.4

3.1

10.0

6.5

14.6 3.8

14.3

8.0 6.6 3.0

7.6

6.5

12.6 14.0 4.8

2.81 M.94 12.81 3.66

3.1 0.57 2.5 1.75 6.9

37.58 2.2 100.00 0.75

9.95 3.27

8.0

7.4 5.4

3.83

3.01

2.18 5.04

12.0 10.2 4.30

2.30

2.97 4.92 2.55 1.76

3.4

30,3

0.39 0.41 0.57 1.54 1.82 1.19

1.66 2.26 2.22 2.78 2.11 4.8 5.36 5.8

9.24

7.17 4.15 5.35

3.8'i

8.73

7.47

20

in»u«ww liwj. n> >»wv.«"»w<wn!|p!(pj!<n»™.i1''1 ■..»,! ll.'H n ■.■,■■!»..'iw».v''-"-M*im

I

H/t

119 119.5 120 121 122 122.5 123 124 125 126 127 128 129 130 130.5 131 131.5 132 132.5 133 133.5 134 134.5 135 135.5 136 137 138 139 139.5 140 140.5 141 141.5 142 142.5

2.13 2.5

0.23

6.1

100.00 2.2 69.47 1.6 5.77 3.1

2.5 1.8 1.3

6.3

5.4

6.8

4.3

6.5

H

9.31 14.6 6.69

8.8

6.25 7.5 13.3 2.75 4.95 0.63 1.26 1.02

1.10 1.76 4.31 1.35 1.22 1.07 1.29 3.45 5.19 16.3 1.76 7.3 7.48

3.68 0.84 2.67 1.32 I 0.80 0.30 6.36 ■'

1.21 ■;

1.37 0.56 1.13 0.42 14.2 i 0.78 9.2 10.5 4.76 3.3 61.4 2.69 22.7

3.06 0.84

■

1.11 ■

3.46 i

3.13 3.09

21

lwn»T«^^">i>'» ; i in ,111.. JI»)HP»«'.J - ->.i. .11. inn -ii II" ..iiutt^-»','«'!!"!1.»'"""""!».!!;!! ii n«i,H:.i w.ini.i" J ;»■ u "« WIMU •"wjwi»|,»iiHWl!llp^im.j|iljiii"»iBlil»p«|u ««i«i •ww^mrwjm

M/«

143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 170 170.5 171 172 175 175.5 176 176.5 177 17715 178 179 180

4.01 3.99 1.36 2.49 1.34 5.04

13.9 0.83 5.4 0.77 .

1.7 1.07 0.79

3.58

2.2 6.4 3.6 2.2

12.0 3.7 9.4 4.3 7.4 4.0

7.1 6.1

0.87 2.08 2.64 2.09 1.69 1.44 0.99 2.69

10.5 3.91 1.56

0.73

3.3

2.52 3.83 4.48 4.27

4.95 4.93

3.10 15.3 2.52

100.0 38.0

3.9

4.0

12.2 10.5 4.9

2.7 9.5 2.7

2.3 7.2 3.4

2.30 2.24 3.61 1.15 0.65 1.00 1.03 0.74 0.80 0.63 0.69 0.77 1.31 2.44 3.84

3.8

4.4

6.14 4.65 7.36 3.34

3.11

3.01 5.24

6.0 8.2

17.1

3.82 2.60 0.77 0.98

6.71 4.92

*

22

/

*W*<Wm JW.WmiMI <!<■ LU»W. »—Wf.'t.U«1* lUHM!.MPllJjpiUH lMg«*IMW«MltlMM.I, # 'm#l.;l-u WI|s«'Pf1

M/e H

1 181 1 T82 1 183 1 183.5 Ü' 184 I 185 - 185.5

■ 186 187

I 183 I 189 1 190

: 191 192

l" 193 194

_ 194.5 195

- 195.5 196

' 197 » 198

; i 199 i 199.5 r

ft* 200

-; V'

2pl 202 203

;■- r 204 205

.;- 206 '■■ 207 1 208 •:" 209

r> 210

i-> 211 212 213

>..'_ 214 V 215

.

i •- -■■

13.1 13.2

10.3 27.2 21.3 58.9 11.2

12.0

2.2 4.3

1.2 1.0 1.4 0.7

9.8 5.4

29.8 5.4

1.6 1.2

5.4 0.76 3.45 6.05 0.72 — 1.55 3.06

8.38 7.1 0.60 10.4 5.5 0.58

3.00 1.77 0.58 0.64 1.53

4.22 4.71

D .5 11.9 14, ,0 16.2 6.1 4.67 4, ,0 5.66

2.33 4.27 r,69 2.90 1.02

5, .4 2.85 4.15

23,1 1.57 2, 5,

.5 ,0

2.59

31.4 1.35 45.0 0.83 2.28 14.7 0.84

5.87 2.04 0.43 0.46 0.89 1.22 0.92 0.88 0.98 1.00

2,59 3.17 7.21 5.53 4.66 3.35 6.60

2. ,9 3.16 5.15 4, .0 2.68 4, ,6 3.37 1. ,2 1.00

0.68 8.0 —

19.4 0.41 4.1 0.58

0.59

23

■ijjjl,ijiilW!i'W"V'VW!|. iji.miiiiii|iili.uiL,ii j_i|»|tnfRi!f^> •Wf'W^IJ.l.HWJII^tjPPJHWP'W.

H/« H

216 217 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 251 252 253 254

2.2

6.5 3.6

100.00 30.5

5.2

5.0

4.6

1.7 1.3 1.3

4.8 5.5 3.2

19.1 3.8

6.5 4.5 9.3 5.5 4.3 2.4

3.9 4.8

1.3 L6

0.64 1.66 1.83 2.88 1.42 1.28 0.89 1.39 2.37 3.40 0.34 0.58 0.77 0.39 0.42 0.42 1.23 5.87 3.98 2.76 1.13 2.54 0.96 3.99

15.2 3.60 0.60 0.30 0.44 0.36 2.12 1.90 1.77 0.60 0.48 0.92 5.57

27.6 0.85

4.7

7.2

2.2

2.1

3.14 4.30 4.93 6,16 6.25 6.16 3.90 2.67 2.52 2.62 2.74 2.54 2.00 1.58 1.68 2.80 5.25

13.8 6.12 4.64 1.56 3.39

4.61 9.44 2.07 2.27 2.33

2.85 4.80 7.42 5.67 2.74 2.85 2.33 2.49 5.17 2.71

2h

mm^—m^^mmmm*m^mr**mim*m™™m

• 'mmmmmmmmam

H/m H

K

235 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 290 291

1.7 1.7

27.2 93.7 22.6 12.7 2.7

1.1 1.1 5.4 6.0

4.3 27.9 45.7 49.1 19.4

0.38 2.05 0.28 0.28 0.27 0.22 0.73 0.50 34.1

13.4 18.8 9.64 3.2 4.63 9.8 11.0

2.21 4.7 3.90 0.70 9.8 2.25 0.39 7.25 0.36 2.67 0.73 5.88 0.43

8.3 2.5 3.5

2.94 1.39 2.46 1.05 100.00

100.00 100.00 30.6 16.7 20.9 100.00 4.S5 2.3 2.82 27.3 2.02

0.41 2.02 0.28 1.56 0.23 1.81 0.35 0.32 0.24

5.00

25

mmm lijjiij^iyflLf.jijj^ijiBji.itJIiJWBW^gWWIIP^ff^llAffL^^^'P™' "• J -'-■ ■-■■■! - ■■' :■ ... «■.!',i*ng»ff|j

M/« R

292 293 294 295 296 297 298 299 300 301 302 305 306 308 309 310 311 312 313 314 315 316 317 318 319 324 325 326 327 328 329 330 338 339 340 341 342 343 346 *47 348 349

9.8 72.9 27.2 2.2

r> 3.0

6.1 3.1 3.9

3.5

1.7

2.1

3.5 1.6

2.46 0.36 4.68 0.29 2.66 0.41 0.50 1.7

0.32 0.37 0.62 0.58 0.39 0.71

0.47 0.27 0.27 0.36 0.60 0.25 0.23

0.73 0.35 1.10 0.85 0.55 0.23

1.37

1.81

2.1 2.2 2.4

2.02

2.3 1.4 2.5 1.3

1.74

26

*m *^Hjm*9l9W '-"H1"-' P'Hl w'j ■! tu.-1 11 mill» ll M. ■ • i t-m«WK.^ m J [^»I j; ■ •'.■WW» ■■ *iy ». >pi.m'M m " P> ,\" i.nn, ■ - WJ Jii... -a EM» W, J-IMMPW-W-, .UI JU n 11 Mii.T«gq?»Wf«TyiPppfWy*ll^l[U I- ' «■■^■T'lPWHWW "^ "'.' *-■! T^WWHipi

PCW—W "'■"

M/e H

i

352 353 354 355 356 35/ 358 359 363 364 365 366 370 371 372 373 374 375 376 377 378 379 380 381 382 383 384 388 339 390 391 392 393 394 395 396 397 398 ?99

400 413 114 «415 416

0.28 0.41 1.5

3.5 4.46 2.9 1.72 43.3 1.69 0.9 13.3 2.62 0.8 1.7 0.85

0.43 0.35

3.98

1.7

4.0 2.4 2.4

1«35

27*7

1.62 1.92 0.50

2.1 1.56 3.2

1.7 1.3

0.38 0.38 0.70 0.67 0.14 3.84

3.45 2.5 14.5

53.4 4.27 16.7 5.39 21.9 1.92 7,9 1.2

0.48 2.32

28.3 8.79 1.35 1.90 1.48 0.25 3.38

3.68 40.2

9.54 1.77

27

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