Document 37BL8ejRQ71aDZEgO5Lmx6EE6

256 VAHDERPOOL STREET NEWARK, NEW JERSEY RETURN TO JACKSON LABORATORY FILE ROOM * NEWARK PLANT PIGMENT COLOR RESEARCH REPORT NEW CHROMOPHORES Period Covered January, 1966 - February, 1967 $5- cr- vs FILE: 223 DATE: 5/5/63 NJ 9340 OUP050027187 KN-67-9 Copy No. 1. Research Numerical Rile 2. Research Office Rile No. 223 3. Library Pile No. 223 4. M. Hunt/E. Gonick, Wilmington 5. W. S. Struve/A.A.Brizzolara .Jo, R.H.Wetzel, Newport 7. P. F.Ehrich 8. H. R. Linton. 9. B.H.Perkins 10. P.J. Monahan (X Pile) 11. C. R.Aldridge 12. Extra 13. Extra 14. Extra 15. Extra 16. Extra NEWARK PLANT PIGMENTS OOLOnS RESEARCH REPORT SUBJECT: New Chromophores PERIOD COVERED: January, 1966 - February, 1967 SUBMITTED BY: APPROVED BY: DATE SUBMITTED: 3/31/67 DATE RELEASED: 5/5/67 RETURN TO JACKSON LABORATORY FILE ROOM DUP050027188 TABLE OP CONTENTS I. INTRODUCTION II. PERIOD COVERED BIT REPORT III. SUMMARY AND CONCLUSIONS IV. PATENT STATUS V. DISCUSSION 1. Xanthenoxanthone Chromophores 2. Intramolecular Hydrogen-Bonded Chromo phores Bis-phenanthridone-quinone (VIII) Fluorenone-analog of Indantftrone 3. Alternate Syntheses of VIII 4. Macrocycle Chromophores 5. Imidazole Chromophores VI. VISIBLE SPECTRA Page I 1 I 3 3 4 9 6 9 10 11 DUP050027189 I. INTRODUCTION This report is a summary of the research on new chroraophores, i.e., xanthenoxanthones, bis-phenanthridone-quinone, the fluorenone-analog of indanthrone, and chlorinated imides. II. PERIOD COHERED BY REPORT January, 1966 to February, 1967 IH. SUMMARY AND CONCLUSIONS The di (N-raethyl) Imide (Vi) of xanthenoxanthone tetracarboxyli'acid dianhydride is an orange pigment. O^N' CHs which shows excellent lightfastness (Fadeometer). The reaction of 3-hydroxy-N-methylnaphthalimide with antimony pentachloride yields VII, the trichloro-analog of VI. VII is a red pigment which shows excellent lightfastness (Fadeometer) and is brighter and stronger than VI. Florida exposure of VI and its chlorinated analogs is planned. Tinctorially, VII is yellower, duller, and approximately as strong as "Monastral" Red (RT-790-D), and It is yellower, brighter, and stronger than "Monastral" Maroon (RT-792-D). The replacement of the four hydrogen atoms in the naphthalene nucleus of the diimide of 1,4,5,8-naphthalene tetracarboxylic acid dianhydride (XXXI) with chlorine produced a bathochromic shift in color. Whereas HH Cl H XXXI H XXXII DUP050027190 -2- XXXI is colorless, the 2,3,6,7-tetrac'nloro-analog (XXXII) of XXXI is a yellow pigment which shows good Fadeometer lightfastness. XXXII is on exposure in Florida. The solubility of 1,5-bis(2,4-dichlorobenzamido)anthraquinone (Yellow 50) in boiling 1-chloronaphthalene and in plastics systems is attributed to the 2,4-dichlorobenzamido-groups being free to rotate with respect to the anthraquinone nucleus. The chlorine-free, phenanthridone analog of Yellow 50, bis-phenanthridone-quinone (VIII) was synthesized because it was expected to be an insoluble, lightfast yellow pigment. VIII was prepared, after considerable difficulty, and found to be an insoluble gold pigment which was brighter and redder than Newport Gold (RT-748-D). VIII showed good lightfastness (Fadeometer) but the synthesis of additional material for Florida exposure was not practical. The fluorenone-analog (XX) of indanthrone is a blue pigment which is inherently weaker than indanthrone. (XX) was not evaluated in lithographic varnish because it readily underwent oxidation to the corresponding azine (XXI). 0 DUP050027191 3 IV. PATENT STATUS No patent applications have been made pending evaluation of the products. V. DISCUSSION 1. Xanthenoxanthone Chromophores The diimide (I) of 4,5,10,11-dibenzo(a,h)phenazine tetracarboxylic acid dianhydride, an attractive yeliow pigment, under goes photoreduction to the N,N*-dihydrophenazine (II) in the absence of air. The relative rate of photoreduction of I, III, and IV in the absence of air is I < III < IV which order correlates I (RH) III (R phenyl) IV (R => 2-chIorophenyl) V (R~H) VI (R * methyl) well with their relative lightfastness order on outdoor exposure, I > III IV. Because photoreduction to II or some related species may partly or largely account for the deficient Florida lightfastness of I, the synthesis of V which cannot undergo re duction to a N,N'-dihydrophenazine was undertaken. The N-methyl analog (VI) of xanthenoxanthone tetracarboxylic acid diimide (V) was prepared as follows; (1) S0& (2) KC1 OH j. G4r CHbNH2(aq.} W CuO DUP050027192 -A- Tiie substitution of antimony pentachloride for cupric oxide in the last reaction yields VII, the trichloro-analog of VI. The structure assigned to VI is based upon the fact that the litera ture reports the formation of xanthenoxanthone tetracarboxylic acid dianhydride from 3-hydroxynaphthalic anhydride and cupric oxide in nitrobenzene. The structure assigned to VII is based upon its analysis, its ability to vat, and the near identity of its visible spectrum with that of VI (See Visible Spectra, Section 6). The reaction of 3-hydroxynaphthalimide with cupric oxide is expected to yield V. 2. Intramolecular Hydrogen-Bonded Chromophores The bis-henanthridone-quinone (VIII) was synthesized as follows: 0 m. - c X Dowtherm VIII (forms red-violet vat) DUP0500271 93 -5- The alternative closure of 1,5-bis(2-oxocyclohexanecarboxyamido)anthracene into the 9- and 10- positions of the anthracene ring would lead to the seven-membered lactam (XI) which is iso meric with the six-membered lactam (IX). IX is the actual product based on Its dehydrogenation to XII whose infrared and visible spectra are similar to those of XIH (prepared by an unequivocal synthesis), and the likely assumption that the infrared and visible spectra of the product from the dehydro genation of XI would be noticeably different from those of XIII. 0 The structure assigned to X Is supported by its analysis, vatting ability, infrared spectrum, and mode of formation. The structure of XIa 'is uncertain but its failure to vat suggests that it is not a quinone.. The structure assigned to VIII is supported by Its relative insolubility in boiling 1-chloronap'nthalene, its vatting ability. Infrared spectrum, and mode of formation. The colors, relative solubilities and lightfastness of VIII, IX, X, and XII are tabulated below. Color Solubility (g/l) Fadeometer Lightfastness VIII Gold < 0.05 g in boiling l-CioH7cl 517 hrs. - good IX Yellow Soluble 24" considerable fading X Orange Soluble 72" slight fading XII Yellow Relatively insoluble 72" slight fading The order of lightfastness,is: VIII > X, XII ;> IX. The poor lightfastness of IX and X (both octahydro-conpounds) is not surprising in view of previous findings that octahydroquinacri- done (from cyclohexanone and diethyl diamino terephthalate) is considerably less lightfast than quinacridone. The greater solubility of IX and X relative to that of VIII Is attributed to the non-planarity of the terminal cyclohexene rings. The inferior lightfastness of xi relative to that of VIII is believed to be due to the readiness of the meso-positions in XII to undergo photo-oxidation. DUP050027194 -6- XIV might be more ligntfast than XII but a practical syn thesis of XIV is not likely. Attempts to prepare XV-and XVI for a study of the effect of substituents at the raeso-positions on lightfastness were unsuccessful. 0 XIV R= F XV R= Cl XVI R~ OAc 3. Alternate Syntheses of VIII The following synthesis of VIII was attempted. XVII and XVIII are violet and red pigments, respectively, and both show poor lightfastness (Fadeometer). For the visible spectra of 1,5-bis( N-l-naphthylamino)anthraquinone, XVII, and XVIII see Visible Spectra (Section 6). Attempts to oxidize XVII to XIX were unsuccessful./ Other attempted but unsuccessful synthesis of VIII follow ( ..indicates the step in the reaction sequence that failed): DUP050027195 7 DUP050027196 -8- DUP050027197 i 9 1,6-Dibenzoylphenazine was ring-closed In an aluminum chloride eutectic melt to give the fluorenone-analog (XX) of indanthrone. The oxidation of XX with acid dichromate yields the bis-fluorenoneazine (XXI). For the visible spectra of XX, XXI and 7-chloroindanthrone, see Visible Spectra (Section 6). By analogy to the formation of "Yellow 100" (l) from 3-aminonaphthalimide and antimony pentaehloride the reaction of 2-aminonaphthallmide and antimony pentachloride should yield the indanthrone analog (XXII). The actual reaction, however, failed to yield XXII. The synthesis of another indanthrone analog, XXIII, from the diimide of 2-amino-1,4,5,8-naphthalene tetracarboxylic acid dianhydride was abandoned after an attempt to nitrate the diimide of 1,4,5,8-naphthalene tetracarboxylic acid dianhydride failed. 4. Macrocycle Chromophores The macrocyclic imide (XXIV) from phthalonitrile and 2,6-diaminopyridine was colorless and, therefore, was evaluated as an ultraviolet absorber. Its lightfastness,. however, was not as good as that of Tinuvin P. The nickel chelate (XXV) prepared from XXIV and nickel acetatewas a tinctorially unattractive yellow pigment. The reaction of 1,3-diiraino-4,5,6,7-tetrachloro{ soindoline with 2,6-diaminopyridine yielded two products, XXVI (presumably) and metal-free polychlorophthalocyanine green. The yellow pigment, XXVI, showed poor lightfastness (Fadeometer). An attempt to prepare the nickel chelate of XXVI was unsuccessful. DUP050027198 10 XXIV R H XXVI R Cl XXV 5. Imidazole Chroroophores The synthesis of XXVII was undertaken because it is an isomer of Orange GR (XXVIII), the brightest of the commercial lightfast organic orange pigments. The dinitration of 1,5diphthalimidonaphthalene gave a dinitro-1,5-diphthalimidonaphthalene, presumably XXIX, The reduction of XXIX was carried out under conditions, iron and acetic acid, that would favor ring closure of the initially formed diamino-compound (XXX) to XXVII. The actual product was a red-brown pigment and its failure to vat suggests that XXVII was not obtained. DUP050027199 VI. VISIBLE SPECTRA - 11 - The absorption maxima (Xmax)>and molecular extinction co efficients (?max) of many of the compounds In this report are as follows: Solvent: 1-chloronaphthalene Imax (mu) sinax Band I. (Yellow 100) N-methyl analog: of I N-phenyl analog: of 1(111) Xantheonoxant'none 450 420 ' r 450 420 24,600 19.400 23*600 17.900 Stl harp 'n-."* " 1 .. -- n " - 450 SS7OT--------------------- "Tf................................ - , 425 19.500 449 To , 700 4g2^0---------167,,9TO0O0------ 505 11,800 II 'O' 11 ~t t it '" -------- "-- 1------- --- ITU x XIX 472 438 546 504 472 437 ....... 480 ' ' -- 49O' XJo definite peaks. 6,100 4,900 Bii road 22,900 16,200 Sti harp 5,600 Broad 2.300 If Incomp.Sol. " . 17,000 Broad At 450 mp. > 10.800 XlirNo definite peaks. At 450 ma C> 6,250 1,5-dianllinoanthcaauinone 12,600 Broad 1,5-bis( N-l-naphthylaraino) xvn anthraquinone .......... -- g5g44g- " 11,500 >16,300 XTOi .... ............................ ~ 543 >1372,j300q00 xx 7,chloroindanthrone - ' 503 24,000 660 8,600 ' 710 106,000 px ! ! ! ' 544 6,500 506 7,100 Broad Bfl road ri iiii 1! xxiv m1 '............. ........... .................... 415 350-400 461 11,500 At 390mu. e* 25,500 22,000 II "It 11 ii r ' .... ..................... XXVIII (Orange GR) 406 49~ 27,000 19,900 tl h " -- ---L -- - YYTX nn Pr*nr?nr>+: 4?0 ----^70^7rp5----- 22,300 r 7rVY"YY II ft ' .IT* ----- ----!--- m m 412) DUP050027200