Document q6djVByKVBOmVkw969Y59qmK

E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOQL STREET NEWARK, NEW JERSEY I KH-51-^5 Serial No. Copy No, 3 Library Pile NEWARK PLANT PIGMENT ..COLOR RESEARCH REPORT JAC&SOlf LABORATORY PIGMENTS GROUP RESEARCH REPORT PIGMENTS PROM DERIVATIVES OP 2-AMIMO-BEOIC ACID AID RELATED INTERMEDIATES (Coat'd.) Period Covered PEBRUARI 15, 1^9 ~ FEBRUARY 1, 1951. " FILE: DATE: 223.2 1/8/52 NJ 97.47 Copy tos X HmerieaX File 2a Research Pil (223.2) 3. library Fil (223.2) *fr Dr. 3* E. Booge. MlUa. 5. Dr. U. Ha Tnlly, Newark 6. Mr. A. Siegel, " 7. Dr. W. S. Strur, Jackson Lab. 8. Mr. A. D. .BA4Angr, " " 9. Mr. J. M. Tinker, * 10. Mr. J. M. fisher, 11. Extra copy Serial Ho. OT5145 Copy Mo 3 JACESOI LABOHATOBI PIGMENTS GROUP RESEARCH REPORT .TITLES PIGMENTS FROM DERIVATIVES OF 2-AMIMQ-BENZOlC ACID AND RELATED XMERMEDIATSS (Coat*4.) PERIOD COVERED? FEBim&BI 15, lM FEBRUARY 1, 1951 CHARGE? A*IX0.236 SUBMITTED BX i APPROVED BTs DATE SUBMITTED? 12/28/51 DATE ISSUED? 1/8/52 DUP050068725 Ws report is a ecmiinuation of H-48-** and k m-49-16 .and covers additional mik don m pigments from anthranilie acid derivatives* Because of the desirable tinctorial properties and the excellent outdoor exposure resistance in metallised enamel and lacquer films, exhibited by the manganese toner of V-chloranttoanilie acid .and beta^osynaphthoie acid <coded Rf-608~D), further investiga tion of substituted amino-bensoie acids as diaao components ms carried out* This work had the Directives of obtaining data to support a patent application and to discover new products of related composition* The work covered by this report .included the following topics - 1. Evaluation of other ^-substituted anthranilie acids as diaao components * 2, Study of effects of position of chlorine Mid other substituents in anthranilie acid* 3* Investigation of soma poly-substituted anthranilie acids* H*. Evaluation of other metallic salts of ^-ehlor-anthranilie acid and of V-nitroantlirani1.1 c acid coupled to beta-oxy-napbthoic acid* !?* Combination of anthranilie acid derivatives with other coupling components * 6. Esters of substituted anthranilie acids as diaze components* 7o Isomers of anthranilie acid as di&so components* 8* Evaluation of quality of 4-chloranthranilie and b-nitroanthranilic acid samples* 9* Study of dlszotisatioa technique* 10* Improvement in baking properties of RT-608-D. Several ^-substituted anthranilie acids (4-bromo-, M-aetfayl-, H-nitro-f and 4-trifluoro rasthyl-anthranilic acid) were evaluated as filaz components la the beta-oxy-naphthoic type of pigment. Of these, the 4-nitro derivative appears to be of greatest value* The maroon produced by conversion to the manganese salt, (KS-275) was much yellower in shade than RT-608-D but exhibited excellent two-tone and was equal to or slightly better than the latter in outdoor durability. This amine is also estimated to be somewhat cheaper than V-chlor- anthranilie DUP050068726 2 Evidence was obtained that substitution, of chlorine in the 4-position, as in 4-ehlor-anthramiii acid, resulted in tinctorial properties and outdoor durability superior to the 5* and 6-isomers. In the case of the nitro group the advantage of the 4-position over the 5- was apparent in respect to tinctorial properties but was not evident in exposure tests. These findings were used as the basis for a patent application. Presence of other substituents in addition t those in th 4-posltion resulted in products which were duller' in shade. acid Several other metallic derivatives of the 4-chloranthranilic BGI dyestuff merit comment. Th# strontium salt (IS-400} was a dark masstone? yellow undertone red with good lightfastaess and bleed resistance. Altho suitable for us in vinyl plastic its cost was too high for this purpose. Chromium derivatives wore generally poor in color retention on outdoor exposure.* However * .a sample prepared in alcoholic medium (8*409) was only slightly inferior to the manganese toner. Equal or slightly superior to th latter were mixed chromius^ttanganes derivatives mad in ethylene glycol (KS~4g 8) and in alcohol (KS-41X), respectively* Only ICS-408 was close to ST-608-D tinetrially The copper salt (KS-4l4) was equal .and the nickel .salt (KS-260) slightly inferior in color retention compared to the manganese derivative prepared as control. However* the latter was somewhat less lightfast on outdoor aqnsur# than th .standard sample of .ET-608-D* leither the copper or nickel derivative was as intense as HT-6O0-D* A number of components* other than beta-oxy-naphthoic acid* were coupled to 4~ehloy and 4-aitro-anthranilic acids and converted to representative metallic derivatives* Of these the copper complex salt of the dyestuff - 4~nlt.ro aathranilie acid coupled to Haphthaail Hb (the p-anisidid of bete-Oxy-haphtholc acid):'"^"me of interest "because of its tinctorial and working properties in enamel systems* This maroon. &S-389. (coded ABT-647-P) is characterised by 4k.,,sgy ton and blue tint and in a metallized film exhibit* egm&lcnt .intensity, and lightfastness, Light reds of excellent lightfastness by Fade-O-Meter test were obtained by coupling the methyl ester of 4-chlor- and 4-nltroayjt.hraailie adds to Maphthanil JEB. Exposure of printing ink fils is being made to .determine their vain as poster reds* DUP050068727 3 Hone of tli isomers of enthraailie acid on of several substituted derivatives which wen tried gave products of note** worthy merit. Th manganese salt of ffi-amisao-hensoie acid and BOW, and the strontium salt of p-amino~bensoic acid and BOH, were yellow undertone reds which were evaluated in enamel and vinyl plastic films respectively hut were found to b inferior to existing products. Quality of ^*elilormithraniX.io acid was found to vary according to the .method of preparation, intermediate obtained in the laboratory by permanganate oxidation of p&ra-ejblor-ortho- toluidin was of much higher purity than material ted at Orcheai by amidation of 2,H dlchlorbehaeie -acid. However, it appears that the amidation process can be controlled to give amine of satisfactory quality* Similarly, H*nitro>anthrsnilic acid was obtainable in pure form by permanganate oxidation of paranitro-ortho-toluldin * However, a more economical method consisting of amidation f S-chlor-Wnitrobonsolc acid is being studied by Jackson laboratory chemists. 4 procedure for dtasotising H-ehlor-anthr.anille acid was worked out. to inverse method in which th solution of the sodium salt with th sodium nitrite is run into hydrochloric acid at 03C has given the best results, b-nitro-anthranllic acid is also readily dia&otiaed by this method* wmmim Use of b-nitro-tothraniiic acid as a component of a BOH, manganese maroon necessitated variations in the process employed in th css of 4-chlor-anthranillo acid, these included development of th coupled soda salt at a boil in the presence of rosin and use of a greater amoimt of caustic soda during the development of the manganese toner* the properties of the product are described above* .Similarly, in the case of H-m@th.yl an&bmllie acid, 'use of excess alkali was required to stabilise the toner (KS-273) during development* the product was only slightly bluer than Hf-bOS-D but was noticeably inferior on outdoor exposure* H-brom-tothranilic acid also produced a maroon (XS-H27) slightly bluer in tint end metallier than fif~608~0 which was inferior in light retention* DUP050068728 frifluor methyl anthraniXic acid gave m a BOI, Ha pigment, a light red (SB-399) which eshiMtad xeoXXent lightfsstness in the Fade-O-Meier However, this did not show any advantage over RT"b28~S> (when tested in vinyl plastic) and, because of the prospective high cost of the -intermediate , is not of practical interest* 2* BOB~!a pigments made from anthranillc acids containing chlorine as a substituent in the 4-, 5-* and ^-positions differ markedly in tinctorial properties and in outdoor durability* Th product from HMhXor anthrsnilic acid (KS-306) is a yellowish maroon., much duller than KT-508-D - the Vehloro counterpart. On exposure it was inferior in color retention. Fro 6-chlor anthraailic acid light bluish maroon (KB-lMf) was obtained, which also exhibited greater color change on exterior exposure* A comparison of the products from 4~ and 5-nitro anthraailic acid confirm the indication of superior color value obtainable from the h --substituted amine. However, light resistance, in contrast to the relationship of the chlor-anthranilic acid pigments, was found to be equally good. Notwithstanding its merit in this respect, til dull ness of the 5-aitro-aathranilic acid maroon would prevent its appli cation as .an automotive pigment, the detrimental effect of the *>nitro derivative was also evident in a product prepared from .mixed % and 5-nitro aathraaillc acid* 3-nitrd-anthraoLili'c acid gave a BOH, in pigment of deep maroon shad which was hard rad weak as a dry color. When flushedinto varnish, an intense blue undertone and tint were obtained which, however, exhibited poor Xigktfsstness. 3o 2-fflino^'-mthyl"5,"CMoro*"bnsoie .acid and 2-amino-1}-- chloro-5-methyl-baasolo acid, the c&rboxy analogs of hake Red C Base and Bed 2B acid,respectively, gave as BQI-M& pigments, dull reds of ' relatively light shad much inferior to the corresponding sulphonic acid derivatives:. A deeper but also dull- product was obtained from a-aMno-^-caor-^-nitro anthranillc acid. From these results and those discussed above, it may b concluded that to obtain the desired type of BOH-m pigment, only the ^--position in 2a&iao~benzoie acid should be occupied by a substituent* $h calcium toner obtained with the car-boxy analog of hake Red C Base was & -dark bluish red having vary poor lightfastness . fh@ amount of Red 2B acid counterpart was insufficient for prepara tion of calcium or other metallic derivatives. DUP050068729 m5 2"aMno3n&phtholc acid, which imy bs regarded as a subs titrated antbrsnllic acid. (in h and 5 positions) produced a BOH Ma maroon, which was darker in ms tom than BT~608*D hut not sufficiently blue or la.tsn.se to serve m a shading maroon. Blonds with RT~608B wore dull and in addition exhibited poor lightfastness on outdoor exposure* ** . A number of other metallic salts of 5fohlor anthraailic acid * 0I wore prepared and evaluated in addition to the manganese' toner. On the basis of rubout and Fade-tHHeter tests none of these possessed lightfastness exhibited by BT~608<=D. The calcium toner, SS307j was a dull maroon which was poor in lightfastness, both in the Fsde-OHster and on exterior exposure* The barium salt* KS3089 was a dull red of poor lightfastness, particularly when exposed to the weather* The strontium salt, ES-^GO is described in the summary. The chromium salt, K-259* was considerably duller in full shade enamel than HT-608-B and mmh inferior in the exposed metallized finish. Efforts were mad to prepare the chromium complex in which the metal is coordinated with th aso nitrogen. Because of the low solubility of the dyestuff in water, other solvents ethylene glycol and ethyl alcohol were also employed. The structure of the result* tug products was not established and it is possible that only normal metallic salts were obtained.. The product mad in alcohol slurry, SS-H-09, was rated only slightly inferior in outdoor durability to the manganese toner but was considerably lighter and yellower in shade. The combined chrcrndtOB-maaganese derivative was also mad, using both ethylene glycol and alcohol as the medium. These were equal and slightly superior, respectively, la exterior color retention compared to the .manganese toner control. Iron, cobalt, nickel and copper all produced maroons of dark masstone and dull undertone which, with the exception of the nickel derivative, were poor in lightfastness in the Fade-O-Meter, However, on exterior exposure tests the copper and nickel toners were equal to or only slightly inferior in color fastness to the manganese control for the series, Unfortunately, the slightly inferior performance of the latter compared to the standard sample of BT"608D leaves this property in some doubt. Excessive reactivity in enamel was observed in the Case of the nickel derivative* t Zinc and lead salts of b-chlor anthranilic acid BOS possessed some merit in respect to tinctorial characteristics (intense full shade enamels) but were noticeably deficient in light- fastness when exposed outdoors* DUP050068730 ~6- f A number of metallic derivatives of the 4-aitro anthranilie **7 BOM were also mad and evaluated by rubout test. The chroiaiuas nickel and copper salts were bluer and duller, in varying degrees compared to the Mu toner XS-275 and were by Fad0~M@ter test poorer in lightfastness. The lead salt was bluer but not duller. However, lightfastness was inferior. As in the case of Vehlor anihranilic acid, the Ba and Ca derivatives were not of interest {dull and poor in lightfastness), The strontium toner resembled the 4-chloro counterpart 5* sgm-sm^m-Si ients 4*chlor, WmthyX, and 4~nitro anthranilie acids were coupled to the following components and the dyestuff converted to the .metallic derivatives indicated. H&phthanils AS, ASD, BL, OL, SW, MX, TB, BG, BO, OP, El, BE. and 1L. Copper .and/or nickel complexes. - Beta*laphthol, Be and Ca salts. * E~sslt Ba, Sr salts. Aceltoacetaalli&e* tfa, Ca, Ba, Sr salt {Wc.hlor anthraailie acid only). Phenyl^Methyl-Pyrazolone, Mn, Ca, Ba, Sr salt. { ) * 2,^"-Pihydroxyquinoline, Si derivative. V Of greatest interest are the maroon pigments obtained from Haphthanll couplings by conversion to the copper complex as disclosed in .416.248 {DuPont). The anthranilie acidIaphthianil AS copper combination has found application in paper dyeing because of its excellent lightfastness but it proved to be too dull and reactive in an automotive type enamel to be suitable for such use. The produet obtained from b-ehlor anthraailie acid m& M&phthanll ASD was somewhat more intense but also exhibited ..pronounced reactivity in alkyd naml systems. Bom improvement in both properties resulted from use of. Saphthanil HL (p-snisidid of BOV)*' However, the most satisfactory combination was found to be 4~n5.tro anthranilic acid and Haphthanil lb. The copper complex of this dyestuff, XS3$9 (ABT~$47~D) ground to an enamel of good consistency. it is characterised by its deep mass-tone and strong blue tint and its excellent gloss both in full shade and metallised films. On exterior exposure it exhibited lightfastness equal to Emhthanll Maroon, RT-566-D, end its superiority in gloss retention, and in resistance to bronzing make it of interest as a blue type shading maroon. DUP050068731 w 7 to Of the other H&'phtfcaails tried, M. merits further study in view of its lower price* Although the maroon obtained with <MKitvo amttoraniXlc acid and this l&phthanil ms yellower sad somewhat weaker than the !KL product* it was similar in other respects6 4ethyl anthranilic acid in combination with HASP -gare results by rubout tests which were comparable to the V-cbloro derivative* lick! and cobalt salt guv lass desirable completes than did copper, usually mush duller* However., more light resistant ZnO tints could b obtained with .nickel. Ho products of interest resulted fro us of other metals * Mn, Cr, Ca, Sr, Bu Couplings of 4ehlor, ^-methyl-, and 4-nitro-anlflmanllic acid to beta-naphthol gave no barium or calcium toners which would repre sent any improvement over like led 33 {anthranilic acid --*gt bets- naphthol, barium salt)* Many ..of the combinations were inferior in tinctorial properties or in llghtfastuess. Couplings of the same amines to E-Salt resulted in two products which possessed some merit* The strontium toners of all exhibited superior lightfastaees compared to Pigment Scarlet lake Mi-211-B but mm possessed equal strength if compared on the basis of equal fly content. She 4-chlor anthranilic acid derivative, IS-367, which was the stronger of the series, exhibited very good lightfastness and migration characteristics in vinyl but was apt of interest because of its inherent weakness* 4-aefcbylanthranilic acid when converted to a lake of Hl~gll~33 type, produced a .much bluer shad product than obtained from antbra- nilic acid. Other properties such as ink texture, baking and bleed resistance, and lightfastness of prints on outdoor exposure were folly equal to BL-2X1-D. Although the bluer shade of this product, K0-368.,' was desirable, the higher materials cost limit its possi bilities. 4-chlor anthranilic acid coupled to acetoacetanilide and to l-pheuyl~3"fflthyl-5-pyr.asolone gave no products of interest when converted to Ba, Sr, Ca and Mu salts. Those derived fro aceto&cetanillde were very weak, greenish shad yellows5 those from`phenyl- methfl-pyrasoloa were of medium shads. Ilckel derivatives of anthranilic acid and N-ehlor- and ^-nltro anthranilic acids coupled to 2,4-dihyfiroxy quinoline were browns of excellent light resistance. The ^--chloro combination was fully equal to Green Gold, fT-562-D, in this respect as well as in representative bleed properties* On the basis of amounts of nickel chloride and NaQH used, these products appear to be complex salts in which the metal is at least partially coordinated. DUP050068732 Tii methyl stars of and 5-ehlor tethrteilic acids and of k* and 5^aitro tethraalllc adds mm compled to representative I&phthaails. Only the combinations of Wehlor- ted V~nifcro amihrteilie acids Kith ll.apht'aaail ME ted of ^-mitro aiithraailic acid with I&phthanil SM mm of particular interest* files mm medium shad reds of excellent. lightf&stness (in fall strength) very similar to the Foster Red, K-1335 <2*5 dichloranillae *- BOL). fbe HASS products, KS-^56 ted *58 ere being exposed ia printing ink films * Whiting lakes were Iso a using these toners hut when tested ia composition linoleum failed to show any advantage over ' existing standard fhe ^substituted anthrteilic acid esters with HMD and .101 gave orange pigments similar in had to Permstone Orange, ttdt-19D0 Hone possessed a distinct advantage in tinctorial properties or .in Xightfastness hut the M-nitro tethranllie ester --* HQL product my merit consideration if *nitr tethranlltc acid becomes available in volume ,. 7* H-aadnohensoio acid coupled to BOH gave only one metallic salt of interest - the manganese toner {KS~b*9). Shis product was a red considerably darker than B3?*525-S> (and slightly lighter and duller than Hf533"'B) with equal lightfastness by Fad0Mtr test. In enamel, however, it was inferior in exterior exposure characteristics. Other metallic salts (Ca, Ba, Sr? li, Cu, 2n, Fb) gave products of inferior lightfastness although the nickel derivative which was duller and bluer than RS-6Q8-D, exhibited only a slight disadvantage in this respect. All were poor in dry texture and were flushed .into the varnish to obtain satisfactory .dispersion. P.aminobnoic acid formed a very dull manganese salt although brighter product of unstable form eotiXd apparently be obtained at low development temperatures. Of other metallic salts, the nickel and strontium toners (la pulp form) mm of some Interest, fh former was somewhat lighter and bluer than Bf-608-D with comparable lightfastness. the latter (KS.^51) was similar in shad and lightfastness to the anthranilic and't-chlor antteraniltc .acid counterparts but because of its poor texture was less satisfactory in vinyl plastics. Other metallic derivatives ware dull or poor in lightfastsesso Some substituted maminobenzoic acids tested as coaponents of BOi, Mn pigments gave the following results. From 3-amino-^f-ehlor benzoic acid a maroon slightly lighter and bluer than 8T-608-D was obtained which, however, was inferior in lightfastness % Pade-O-Mefcer test. 3-amino-Vmethyl benzoic acid gave a yellowish red - even yellower in hue than obtained from the unsubstltuted M-amino benzoic acid* fhe corresponding methosy derivative from 3-amino~p-aaisic acid resulted in a dull blue shad maroon of inferior lightfastness. DUP050068733 -9 - On substituted p-asinobensote acid (4-aMno-3nitro benzole acid) gave a brown BO!Mq derivative of no interest* 8 issaUjauzt MM, 4CMor-anthra3xLlic acid mad by permanganag oxidation of para-chlor-ortho-toluidin was obtained in the laboratory with a purity of 97-100$ (nitrite value)* Melting points ranged from 231*234 to 23623?0 (uneorreeted)* A charge mad in the Mewark seai**works and deacetylated at the Chambers Works was of similar quality* However, yields by this route war economically low* the Intermediate initially mad at '-Orchem by amidatios of 2,4 dichlorbenzole acid was of lower purity, nitrite value 90-96J&. The impurities - 2,4 dichlorbensoio acid and probably some 2,4 diaaHnobnzoic acid - interfered with diassotizatioa and when present in sufficient amount resulted in Inferior durability of the BOH, Ma Maroon, Rf-608-0, Subsequent modification of the process have yielded intermediate of greatly improved quality. 9. Direct diasotizatioaa of 4-cM.or-anthrani3.ie acid by addition of sodium nitrite was not successful due to the insolubility of the amine in acid medium* 0s of an agent such .as sodium xylene sulfonate increased the rat of absorption of nitrite but was not considered practical because of the cost. Blazotlzation by rapid addition of the acid to the alkaline solution of amine and sodium nitrite was saiisfaetory0on a small laboratory scale and when pure intermediate was used* However, increase in charge sis with the less turbulent agitation prevented immediate diasotlzatiaa of the win and resulted'in a considerable amount of undiaasotlsable material* Best results were obtained by m inverse method in which the solution of the soda salt and of sodium nitrite (at 30-35C) is run into hydrochloric acid <3.3 mols) at 0"30. So t o ua&iasotised residue (about 2$) is usually obtained even with amine of good quality* This has been identified as partly 4-chlor-mthranilic acid .and partly diazo-amino compound. When intermediate of poorer quality is used* the residue filtered from the di&so is greater, amounting to 10-15$o 4^litro-anthranilic is also readily diazetized by the above procedure. It was necessary, however, to increase the volume of the soda salt solution to avoid precipitation of the amine, 0s# of a higher temperature my have the same effect* DUP050068734 Kf\) : Sl-iiG * 10 * xo. The maroons from substitutscl-aathranilic acids exhibit tfe@ poos? baking resistance of BOS* Km maroons Some improvement,in -the case was obtained by formation of the Me salt in alcohol slurry instead (of of water* However, results were inconsistent and, since the pro* (B-608B eedure was not economic., this lead was abandoned M1K1 Details may be found under the following references:. |V>Chlor*-.anthraiiilic AeidTj, AcetoaeetanHide H*B, 1353 , Exp. 49 Beta laphtliol B.B* 1353? Exp* 1 Beta-o:y*naphthoic acid. Various metals lf.Be 1320, Exp* 31? 32, 43? ft? 62, 63, 64, 65? 88, 69? 70, 71? 72* Process variations Quality of amine B.B. 1336, Exp* 56 H.B. 1353? Exp* 20, 23, 28, 56, 62? 76* I.B* 1370, Ixp 25? 28, 31 32, 34 H.B* 1353, Kxp* 20, 41, 43? 45, 48, 50 * H.B. 1370? Exp. 9? 10? 11? 12, 23? 24? 35? 42, 43, 53? 55* 1Bb 1336, Exp 14, 22, 42? 85* .B* 1353?. Exp* 13? 27 ? 75# H.B* 1370? Exp* 29? 40. I.B* 1385, Exp* 11? 12* 2,4 Pihydromy*Quinoline B.B* 1396? Exp* 14* --$> flaphthanils HB. (1353)) Exp* B: S: 35, 73, if; *: II: Hienyl-a^thyl-pyrasolon i.B* 1353? EXp* 52* --ta-Ssit H.B, 1353? &*p 7? 15a DUP050068735 n ^C&Xqi?~aatteaiaiile AcidJ 3%i;a-o.xj~nsphiholc meld *--> lapathanils Y ^6-CM.or-aattoanilie Aci&J ff.fi. H.B* 1338 , 1353, B$&JCpp*<5 55* 17, 88 18, 19, f.B. X292?- Exp, 31. I.B, 1353, sp. 35. "*>> Bt-=osjnaphtliGio acid lapM&aaiX / SD >/ |SClilo?"5,wdao'fera:Oic acid] I,B. 1279, EXp. !! .13, 1338, ep. ?, 80. 35, I.B, 1353, Exp. 35. ^ l&p&thaaXXs / lt-'Bx'om-aatfccc*aiiiXic Acid Bet&<axy^aapiitlioic acid [VMethjXaiitteaiaiilc lcid\ if b 1353, Exp. 9 I.B. 1370, Exp. 66. 1 ,B 1370, Exp. 46, N.B. 1385, Exp. 5. --Bets-Iaphtlml *""*7 Beta-oaEyHaap&thoic acid laphtlmnil ASP'/ -- B-SaXt 3"*Iitro*"attoaailic Acid '~-7 Beta-oxj-aapht&oic acid pv-Hltro-anttiranillc Acl^ I.B* 1353, Exp, 1. I.B, .1320, Exp. 4-2. I.B. 1338, Exp, 23, 27, 38. I.B* 1353, Exp. 30, 34, 40. I .Be 1353, Exp. 7, 15* B.B* 1385, Bp# 23o Beta^oxy-aaphilaoie acid --Beta-Iaphthol HapfcthaniXs f.B, 1320, Exp. 4-2, jr.fi. 1338, Exp. 21, 25, 26, I.B, 1353, Exp, * 41, 62, jr,. 1370, Exp. 17, 83, 70. I.B. 1385, Exp. 1, 36. I.B. 1353, Exp. 1. I.B. 1353, Exp. H.B. 3353 # Expo I.B. 1370, Expo I.B. 1385, Exp. 7, 15. / $ 3, I. / DUP050068736 - 12 - jlj-Bi t?oaiatbranllie Aei&J Bta-sy^pht&oic acid faplitlmniX y I.B. 1333 8*p. 62, 80 :I,B, 1353* B*|>. 24. 3? 3, 1370, Mxpa 30 , 33 H.B, 1370, Sacp. 36. l^frifl\B>x^athyl-2"ejalno]3Sjas502.c Acid mmf Bsta^ossy-fxaplithoic acid H.B. 1320, Bxp. 9 2iuaJ,no^^Htliyl "5"Cblos*"l>ag;olc Acid Beta-oxy-napiathois acid H.B 1353, Bxp. 2# H.B. H3. 1370, 1385, Byft,rx,,. .p,, . 72. 4?* 49. a-A^I^o-^ciilor-f-matlayl-semvoic Acid --Beta-o3qr4iaplit'ae:lo acid 13. 1370, Bxp. 5, 6, 72. 2- Aaino-^-c1:Lor-5"R.ltro-b@^soic Aeld --Beta-oxy-ssplithole acid H.B. 1338, S&p 73* M-to'd.aol>@asoie Acid B.eta-xy~mpht3toie acid H.B. 1385, Bxp 13, 17, 18, 28, 29. PiiBiaobasolc Acid --> Beta-ozF-aapb.tIioie .acid H.B. 1385, fcp. 13, 3,4, 15, 20, 28, 29 3~Jiao4-el!loi?o-|}as0ic Acid --^ Beta-oxy-imp&t&oi c acid 13. 1385, !xp* 19, 3 45* 3- Aiain-4-Eithoscy-bcaisoio Acid ^*Beta*o9Qr*anp3ithole acid 13. 1385, Ssp. 23, .30. 3- Amino-4-3TOt^l-Baoi0 acid --^ Bsta-oxj-ns.plitiioic acid 13. 1385, Bi$* 19, 30. 4- Asiino-3nitro--'ba?isoic Acid Bata-oxy-mphthoic acid W.B. 1385, Sxp* 45. 2-AMao-3"Haphthaic Acid --> Beta-oxy-mphthoic acid H.B, 1353, Exp. 38, 41, 67. DUP050068737