Document YVQ313nkLxnKXRmg27aJERvN

E. |, DU PONT DE NEMOURS & COMPANY PISMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Serial No. Copy No, KN-53-9 1 Numerical File V) Period Covered NEWARK PLANT CHEMICAL DIVISION - COLORS JACKSON LABOBATOHT PIOMSBfEPS GROUP RESEARCH REPORT AZINS PIGMENTS NOVEMBER 13, 1951 to APRIL 14, 1952o TO (Y w NJ 9747 RLE: DATEt 223c6 5/7/52 N41998 Serial Ho, KN-53-9 Copy Ho, i Copy toe 1, numerical File 2, Chemical Division File (223,6) 3, Library File (223.6) J. H, Ttilly/A. Siegel/Library 5, W. F Spengeaaa/Llbraiy 6. W, S. Struve, Jackson Lab., Qrcftem, min, ? F. M. Tinker, * n D. C. Hiller, Development Section, Chambers Works, Orchem, Wllm. 9, Extra 10. Extra JACKSOW LABOMTOay PIGMENTS GROUP RESEARCH REPOISP m VitmSBl Hoviia 13,1951 to Aim i**, 1952. CHARGE: A-II-C-275 SUBMITTED BT* A. D. Reidinger DATE SUBMITTED t **/W53 DATE ISSUED# DUP050069288 imomTOii The belief that the excellent lightfastness and bleed resistance of pigments of the Indanthrone class ware related to their structure which permits a high degree of charge separation, hydrogen bonding and of resonance, suggested the possibility that new pigments of similar properties might be obtainable by adopting some of the structural characteristics of the Indanthrone*. inspection of the structural formula for the latter showed its resemblance s 0 to substituted dibydrophenazine and it a (Chemical Abstracts numbering) accordingly appeared that other phonazine derivatives might be found which would he of value as pigments. s o mma h y MD comgsiomt 1,6 Dibenzoyl-5,10 dihydrophen&zine was a violet colored substance insoluble in water but quite soluble in benzene. It was unsuitable for pigment use because of instability in the presence of oxygen. When rubbed out in lithographic varnish it was oxidized quite rapidly to the yellow ezine fora with retardation of. drying. DUP050069289 The corresponding 1,4 derivative appears to "be even store unstable. The violet product obtained by reducing 1,4 dibenzoyl phenazlne with ammonium sulfide Is soluble in alcohol and on standing at room temperature soon fades completely. Two other derivatives in which one of the reactive hydrogen atoms' were replaced by a phenyl group and the other bonded by nitro and carbonyl groups (l-nitro-3-chloro-5~phenyl-5,10 dihydrophenaslne and 1-benzoyl-5-phenyl-5,10 dihydrophenasine} were red shade blues or violets which were also sensitive to oxygen and soluble in organic solvents. It is of interest that the nltro substituted color was greener and stronger than the benzoyl substituted product# In view of the difference in stability and in solubility between the dibenzoyl dihydrophsnazlnes and Indanthrone, which was ascribed to the benzoyl groups, attempts were made to prepare a comparable product of the following type by condensation of dl- or trlbromofXuorenone Br However, only small yields of a black product of uncertain composi tion could be obtained. DISCUSSIOHt 1,6-Dibenzoyl phenazlne was obtained in rather low yield by condensation at SlCr'C in trichlorbenzene of two molecules of g-brom-3* amino benzopheaone# The latter Intermediate was prepared by the following route - 3-nltrophthalic acid -- * 2-bromo-3-nitrophthallc acid 0 2-bromo-3-nitro-benzophenone --^ amino compound, Reduction of 1,6 dibenzoyl phenazlne to the 5,10 dihydro form was easily accomplished with sodium hydrosulfite and sodium hydroxide In alcohol. As stated in the summary, re-oxidation to the azine form also occurred readily. DUP050069290 Condensation of 2-brom-3-amino benzophenone with the parent nitro-coiapound did not proceed satisfactorily in ethylene glycol or in alcohol# l,4Pibenzoyl phenazlne was prepared in the following steps: cyclohexanone --7 cyelohxafc@-l ,2 dlone (+ o-phenyienedlamlhe) ****$ 1 >2>3 ,4-tetrahydrophenazine (4- bsnsaldohyde) 1,4 aibenz&l-2,3- dlhydrophenazlne --^ 1A dibenzyl phenazlne product* It is of interest to note that the condensation of 1,2,3,4 tetrahydrophenaaine and benzaldehyde is reported in the literature reference (JCS 19379 1701) to give the dibenzyl derivative II directly* rather than the dibenzel phenazin 1* II %c *c 6H5 m*c 6h ^ H C.CgHj M.p . 152-154 (lit 158) M.p. l42~l45 However , the inability to oxidize the* initial product to the dibenzoyl derivative, the evidence of ultra-violet absorption curves, and finally the successful isomerization to the desired demonstrate the reverse to be the ease* Preparation of 1,4 dibenzoyl phenazlne was also attempted by the following route - paraxylidine (+ o-nitro chlorbenzene)---> 1,4 dimethyl-2 ' ni trodiphenylamin (with iron --*7 1,4 dimethyl phenazlne --7 1,4 dlcarboay phenazlne --$ product* however; the oxidation of diethyl phenazlne was unsuccessful and the met was abandoned* Another route to 1,4 dicarboxy phenazlne (pyroeatechol (+ XBC03) --7 2,3 dihydroxy terephthalic acid (+ o-pbenylen diamine) --product) was not pursued because of low yield and impurity of product resulting from the carbonatlon step* Phenazlne was obtained In fair yield by heating 2-nitro diphenyl amine with a mixture f iron powder (reduced iron) --* iron filings. Use of some reduced iron was necessary to in the reaction* DUP050069291 - 4- - nitration of phenazlne gave the 1,3 dinitro derivative which upon heating with ammonium sulphide was selectively reduced to 1*3 dinitro-5,10 dlbydropbenazine. The product was a bluish black substance almost insoluble in organic solvent but which according to the literature also tends to roxidize and become yellow* The attempt to make an Xndanthrohs analog from di- or trl~ brom-aminofluorenone involved the following steps? - fluorene --v 2-nitrofluorene --2-nitrofluorenone --> 2-aminofluorenone ;--y (1,3) dlbrom 2-amlnofluorenone --*ja product* Bromination of 2-aminofluornone gave a mmo-bromo-derlvative believed to be 3-bromo-2-aminofluorenoas and a dibrem (probably 1,3) derivative. Trlbroxa-2-amlno-fluorenone was made by bromlnating 2-aainofluoren hydrochloride and then oxidising to the fluorenone counterpart* condensation of these derivatives by the Oilman method did not proceed with the ease exhibited by the comparable bromo-aminoanthraqulnones and no products of merit were obtained. This may be explained by the relative inactivity of the bromine atoms in the fluorenone molecule as reported in the literature. MPERXHBNTALBMAXIiS? Methods of preparation and results are recorded in N.B.1290, and 2S.B.1430, 1325, 1398. The main literature references are listed below* Phenazlne from 2-oitro and 2-aimlno-diphenylamjLne. Waterman and Vivian. J. Org. Chem. l4-.289 (1949) .............." -..... *- -......... Phenazlne from 2-nitro .diphenylamine. .V&a2Slack & Slack. Saiag.-tf.QA3Z Methoxy, dimethoxy phanazine. P*>* Station JL^l -_(19^1 Heterocyclic Stable Free Kadieal and Precursors* KIm. Clmrk & flayls J.C.^^ l9,. 3Qia 1,4- dihydroxy phenazlne* DUP050069292 -5- 1-nitro phen&sine ,, 1,3 dinitro and 1,3 dlnitro-dihydro phsmazin. tan. 558. 10-34 (17) Phsnazine 2,6 dicarboxyiic acid, JUs&vJ 1:2*3 :4 Tetrahydro phen&sine. 1 Methyl, 1:2:3s1* Tetrahydropheaaxin. Phenazin l-earhoxylic acid, alley, et al. J. Chem. Soc. 1932, 1895 Bull. Soc. Chim 12 , 506-16 <1945) Bauh, et al. J. Org. Chem. 10,201 (194-5) Cyclo-hexane-l:2 dlone. IteUMte* 1,4- Dibsnzyl phenaain. Other phenazine derivatives. Praxmarar, Monotshefte 28, 1207 <1906) Hemmelmayr Monotshefte 38, 82 <1917) Catechol diearboxylie acid Diels. Ber. 31*-, 1764- (1901) Fluoren --2-asdnofruorenon. Anal. Asoc. auin. Argentina 33, 35-40 (C.A. 40S14-792) fcaidaefcA^.. Nitration of fluoren Eckert & Langecker. J. prakt Cheanie 118,263-81 J. Chem. Soc. 194-9, 2020 Courtot & Vignate. Bull. Soc. Chim, 4-1, 58-64 Huntres, et -al. J.A.C.S. 64-, 284-5 (1942) te3..B..4s.P.,t foamy ArKe3fclm>,5,, Brom-amino-fluorene and -fluorenone. . MPH DUP050069293