@i,913,749 a i@mperat7ure of @bout 300; C as OthetWise some of the crystallit(@d Steb@ins acid may go back- into solution and isomerize, thereby decreasing the yield. In diliitilig I the completicn of the sulfonation mixture ' at 1 the sulfonation, the sulfonation inixture ma3, -also be added to water efficiently cooled and agitated so that the tempbratu@e 6f the diItited inass does not exceed abolit 250 C. Inio stead of Filter Cel other equivalent filteii aids may be emplo-ved io assist in the reinoval by hltratioii of ., the small aiiiount of finely di'Vided inaterial present in stisoeiision in the clilution mixture. The Stebb-ns acid may 15 be salti@d out of the dilution mixture by other suitable alkali-Metal salts, c. g., 1)6tassilliyl chloride, etc., and the Stebbins acid alkalimetal salt may be filtered at 6ther temperatures. A filt@ation teinperature not exceed2@O in- about 2@50 C. is preferred, 1-iowever, )n oraer to prevent undtie 16ss of product by soluti6n in the inother liquors. The inventi6n thus affords a means of seetiring an increase iii the yield and in the 5 bbins acid,-D 4uced from betapuritv of Ste ro naphthol by sulfonation with stilfuric acid Since certain changes inay be inade in the process above@ described without departing from the sco@e of the invention, it is intend30 ed that all -nlatter contained in the above deser.ption sliall be intei-preted as illustrative an@4'not in a limiting sense. It'is al-,o to be uiiderstood theit @the following claims are inteiided to r 6o@er ,ill of the gen@6ric aiid specific features o@f the invention herein described. I cillim l@ Tn the I)rocess of pr(@paring,, Stebbins acid bv the sulf onat,ion of beta-na@lith6l with 40 Nem.@nt concentrated stilf ui@ic acicl, the impr6 which co prises rei,n I oving froin the spliere of the reaciion, a@ soon aq possidie, the Stobbins acid formed. e p@oces@ of preparing Stebb' 2 In th ins ,teid by the sii1fonation of- I)eta-na phthol with concenti-ated sulftii@ic acid, the imi-)rovem6nt -w@ich coniprises iiiducino,, crystaliiza-tion of Stebbins a,cid f roill the i@eacti;n ii.-iixture suibstan.tially as soon as ti-le react@ion mixtiire beCoTnes supersatur,@ted tl-iet@with. 3. 11-i the 13rocess of prephting Stebbins acid by't-he s Lilf onation of betaiiaphthol with concentr,,ited s@lf uric acid, the iinprovement @vhicb. coin@riseq seie'din- t,he @ea(-.tion mix65 ; I stibsta@tia-113, as soo@ as it, Decoine-s sa,ttir@ied'with Stebbiiis acict 'to cause the Steb,bins aci@l f orme @d to cryst,,illi ze. 4. Iii the i3ro@ess of pi@epariiio- St,ebbins 11 9: 60 icid by the, stilfpn,,Ition of-@beti-naphtbol ivith concentrated stilfi-iric acid. the iiaprovel-nent which conlprises adding a crystal of Stebbiiis acid to the repetion mixture ds a seeed @ubstaiatially as sobn as tile reaction inixtilre be65 comes saturated witb Siebbins acid@ ivherebv th" Stebbins acid f ori-ned is caused, to crystallize. 5. Iii the process, of preparin . Stebbins I 9 acid by the' siilfon,,'ttion of beta-naphthol with coricelitrat d @i-ilftiric acid, th ' e iiiiprovement '70 N),Iiich eoiiiprises aclaing a c.rystal of an alkali-iii(@,tal salt of Stebbins a6id to the reactioii iiiixttire as a seed substantially as @oon aq the re,,ictioi-i@ illixttire becoiiies sattirated inrith Stebbiiis acicl, wli.ereby the Stebbi-ns acid 75 'foi-iiied is caused to crysta-Ilize. @6. In the process of preparing@ Stebbins t qlcid by he stilfonatioii of bet-a-iiaphthol with c oncentr,,ttecl. stilfuric acid, the iniprovement Nvhich comprises adding the beta-naphthol so to the sul.f.Liric a(@id wit,hii-i a peri6d not exeeediiig 5 li'liniites, aiad causiiig the Stebbins acid to crystallize f roin the reaction illixture slibstanti Ily as sooia as the reaction mixture becomes sti.persattirated therewith. 85 7. In the @pi-ocess of preparino,@ Stebbins ilcid by tlic, sLil.f6nitioii of betanal)lithol with colicentr,,tted sulfiii-ic acid the iinprovement ich coniprisee@ '"7h , rtpidly'addiiig tl-te beta i-ilphthol t tl-ie stil@ur'j acid pre-cooled to 9(, 0 1 It t@ilipertture, n6t elxceedino, 5o'C. and com@ 1.)leting the siilfonation @at a temperattire not e-Neeeding abolit 25 lo C. 8. In the pr6cess of prepai-ing St-ebbins acid b3, the stilf onation of beta-in a,phthol with fl@j@ conceiitt,cited sLilftii-ic acid, tl-ie@ ii-nprovem'ent %vliieh conipiises rapidly addino, tlie'beta@n n,,iphthol to ti.le stilftiric acid pre-cooled to Itiot exceediiig abotit 5' C., C a, te,'-"Perature I OMpleting tho sulfonttion at a ten-iperafure of I( abotit @Oo to 25o C., @iid adding the completed s-Lilfoi-i,,tt-ion niixttire witlio@t delay to ice wat6i-. 9@ The pro-,ess of prepa-vino,, Stebbins acid %,hich coiiipriz@es acldiiig ivithiii a. p6riod not exceedinz 3 minutes about 100 @parts by 'vveight of beta,-naplitliol t6 abwit @00-2@b pai@ts b@- weigb.t of 98 to 100 @er (@ent. sulfur@ic a Lir cid ivhile @reveiiitin,g the teii-ipera-t P, f'rom exceeding aboui. 2,5' C., and C.,tusinv the Steb il' bn,@ acict to crystallize from the redetion n-iixI re ubstaiitially as soon as tl-ie nixtu s tui-e becoi-nes supersaturatecl tlierewith. to. The process of preparing Stebbins'acid 117hicli coml)rises t,ddiiio, withiii a period not liL@ xceeding abotit 5 iiiintites about 1.00 parts by e weight of beta,-naphthol to about 20OL280 )arts by weigl-it of about 100 per cent, sulftiric cid, while 1)1.eveiitill,- tl-ie t@mperatlire from exce@dinz iboiit 2,@@' C., and adding a crystal of Stebbins acid to the react@ioii n-iixt.ui-e as a S66d about 8 to 13 ininutes after the betanaphthol hts 'all been added, whereby the Stebbins acid f oriiied is caused to crystalliz4e@@ 11. The process of prep,,triilg Stebbins acid which comprises adding within a period not exceeding about 5 minutes aboiit 100 -Darts by weiglit 6f betanaphthol to about 200-230 yoarts b.17 weight bf about 100 per ceiit. stiliuric@a@id@cooledtoatemperatureofabollt5,
4 1,913,748 C., adding- a crystttl of Stebbins acid to the reaction mixture as a seed about 8 to 13 i-ninut6s after the be'tanaphthol has all beeii added, whereby tlie. Stebbins acid forn-ied is -,aused to crystallize,, ancl continuidg the sulfonation until substantially all of the betanaphthol has been sulf onated. .1 12. The process of preparing Stebbins acid which -0'1-' 'rises addin- within a pei-iod no'u ' 10 i ceeding al-out 5 minu-tes abotit 100 p,,trt by -.X s weight of beta-iiaphthol to abotit 200-230 pdrts by -%veight of 98 to 100 per ceiit. sulftiric acid while preventin@2@ thetemperature from exceeding about 25' C. and causing the Steb@ins acid to crystallize froiii.the reaction inixttire substantially as soon as the reacti6ii tnixtiire becomes stipersatlirated tlierewitli. 13. The process of preparin,- Stebbins @icid which comprises adding within a period not 20 about 5 miliiites aboiit 100 parts bl, 'Weiglit @f beta-naphthol to about 9,00-9,9) parts by weight of about 100 per cent. sulf itric acid cooled to v@ temperatlire of about 50 C.@ addino, a er I stal of StebbiTis acid to ttie y 25 -eacti u on mixture as a seed abo t 8 to 13 ininutes after the betanaphthol has all beeii added, whereby the Stebbins acid fcrmed is causecl to crystpllize, continuiiig the sulf on,-,tioh until substantially all of the beta30 @iaphthol has been sulfonated, wliilc-, preventing the tenipera'ui-iro fr6in oxcoedin@2@ about 300 C dilutin(y the resulting sLill'o-natioTi ii,ii,kti,ire with cold water without del-- Y, aiid sepai-,,ttiiig the @Stebbins acid. 35 14. The process of preparin Stebbiiis acid 9 which coliiprises adding within a periocl iiot exceding about 3 minutes about 100 parts by Wei,-lit of beta-naphtl-iol to about 200-230 .1 @irts b oiit 100 per cen . p y ivbight'of ab t siil40 furie, acid cooled to a tein erature of ,ibout PI 50@ C., adding a crystal of St6bbins acid to the r,-acl@-ion mixture as a seed about 8 to 13 ii-iinutes after the beta-iiaphthol b.as all beeii added, wliereby the Stebbiiis acid forin(@d is 45 -aused to erystallize, cont;.D.uing the stilf ojii ti6n at a temperature not exceeding 30' C. for about 30 mintites after all of the betanaplitliol has beeii qdded, and dilutin(,, the ilesi.ilting sulf on-,ttion mixt,,ire without delay 50 -@,vhile prei,entin- the temperattire from ri-@i--ng above 25' C. 15. The process of preparing StebbiTis tcici Whi6h coin I prises adding -within a period, iiot exceeding @ibout 3 inintitesibout 100 parts by r)5 -,veight of beta-naphthol to about 200-230 parts by w6ight of about 100 per cent. stilfuric acid cooled to a teml,)erature of about 5' C.) addin(y a crystal of Stebbins' acid to the reaction n-iixttire ,@s i seed about 8 to 13 iiiinutes co after th6 beta-naphthol has all beel-i added, whereby the Stebbins ,tei-d formed is cail@-@ed to crystallize ' cont;-n,,iin,- , the siilfonation a'Ll a temperature not exceeding 25 0 C. for about 30 minutes after all of the beta-iiaphthol h,,,ts 05 been added, diluting the resulting sulfonanion iiiixture without delay while preventing tl-ie teinperature from rising above 250 C., and salting out the Stebbins acid. 16. The process of preparing Stebbins acid which comprises addiiig within t period liot exceediiig about 3 minutes about 100 pai-ts by weight of beta-naphthol to about 215-220 parts by weiglit of 100 per cent. sulfuric ' acid cooled to ateiiiperature of about 5" C., adding a crystal of Stebbins ae'd to the reaction 75 I mixture as a seed abotit 8 to 13 minutes a'l.ter the beta-naphthol has all been added, whereby the Stebbins acid f ormed is caused to ervst,@tllize, continiiing th-, sulfonation at a teiuperattire not exceeding 30' C., for about 30 80 ininutes af ter all of the beta-na _phthol has b,-eii added, while preventing the teiiipera7 ture froiii exceedino, about 301 C., diluting the resulting sulf ontlion mixture without clelay while preveiitiii tl-ie teinpei-ature -L'rom 85 9 ris,.ng abov(- about '@50 C.@ filteriiig off insoluble in,,iterial, salting out tl@e Stebbins acid by n-ieans of sodium chloride, and separating tl-ie Stebbins acid sodium salt. 17. Iii ' e process of preparing Stebbili uh $90 acid by siilfonating beta-naphthol with concentrated sulfuric acid, the improvement which coinprises reinovin@y the Stebbins acid foilmed fi-om the sphere of reaction by causing it to crystallize out of the solution whilo 05 continuin- the stilfoiiation of the beta-na h2@ p thol. 18. In the process of preparing Stebbins acid, by sulfonatina beta-naphthol with concentrated sulfuric acid the improvement '10( which comprises adding crystallized Stebbins acid t6 the reaction mixttire substantially as soon as it becoines saturated therewith, s whereby the Stebbin acid forrned is caused to crystallize, and Continuin,- the sulfona,- 105 tioii of the beta-naphthol, the Stebbins acid continuing to crystarize out as formed. 19. The process of preparing Stebbins acid which comprises rapidly adding about 100 parts by weight of beta-n,,tphthol to about l@10 200-230 parts by ivei-'@it of 98 to 100@'o sulfuric acid while prev@ntiiig the temperature from exceeding about 250 C., and causing the Stebbins acid to crystallize fron-i tl-ie reaction mixture about 8 to about 13 minutes 115 after the beta,-naphthol has all been added. 20. The process of preparing Stebbins acid which comprises adding witliin a period not exceedin- about 3 ininutes, about 100 parts by weigi@t of beta-naphthol to about 200-230 120 parts by weight Of 98 to 100@'o sulfuric acid precooled to a temperature not exceeding about 50 C., and causing the Stebbins acid to crystallize from the reaction inixture about 8 to about 13 minutes after the beta-naphthol 125 has all been added, while@ maintaining a temperature not exceeding about 30' C. 21. In the process of prepariiig Stebbins acid by sulfonating beta-naphthol with concentrated sulfuric acid, the iniprovement 130
i,913@748 which cqmprises reirioving the Stebbins acid f,ormed from the sphere, of the action by causing it to crystallize out of s6lution substantiallv as@soon as the reaction mixture becomes supe I rsaturated therewith, and coii' tinuing the siilfonation Of the betanaphthol at a temperature not exceeding about 300 C., the St@bbins acid contiiiuino-, to crystallize oiit as formed. 10 22. I:n the process of preparing Stebbins acid by sulfonating beta-naphtliol with concentrated stilfuric @cid, the improvement wliieh comprises rapidly addin- the betanaphthol to 93 to 100@'o sulfuric acid pre@j cooled to a temperature not exceecling about 15- C., causing the Stebbins acid to crystallize from the reaction mixture about 8 to about 13 min-Lites after the, betanaphthol has ,tll been added. and continuino- the sulfonaI the Ste i s acid (.0 tOn of the beta-nap n I continuing to cryst out as f ormed. 23. In the prcicess Of prepariiig Stebbins acid by E;ulfonating beta-naphth6l with cOncentrated sulfuric acid, the improvement which comprises rapidly adding the betanaphtliol to 98 to 1:00@'o siilfuric@ acid precooled to a tempei,ature n6t exceeding about 5 o C.' causing the Stebbins acid to crystallize from the reaction mixture about 8 to t) @ibout 13 minutes after the beta-naphthol bas all been added, and continuinz the sulf6nation of the beta-naplithol at a teiiiperature ii6t exc@ceaing about 300 C., the Stebbins acid continuing to crystallize out as formed. In witness whereof, I have hereunto set MY hand. WILLIAM J. COTTON. 40 45 50 55 60
