USRE23024E - X-dimethylaminophenyl - Google Patents
X-dimethylaminophenyl Download PDFInfo
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- USRE23024E USRE23024E US23024DE USRE23024E US RE23024 E USRE23024 E US RE23024E US 23024D E US23024D E US 23024DE US RE23024 E USRE23024 E US RE23024E
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- 239000000243 solution Substances 0.000 description 26
- 239000002253 acid Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002596 lactones Chemical class 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NEGFNJRAUMCZMY-UHFFFAOYSA-N 3-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC(C(O)=O)=C1 NEGFNJRAUMCZMY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N Methyl iodide Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- -1 4-dimethylaminophenyl Chemical group 0.000 description 1
- DPTAYXRMLJNOCN-UHFFFAOYSA-N 5-(dimethylamino)-3H-2-benzofuran-1-one Chemical compound CN(C)C1=CC=C2C(=O)OCC2=C1 DPTAYXRMLJNOCN-UHFFFAOYSA-N 0.000 description 1
- IPAJDLMMTVZVPP-UHFFFAOYSA-N 6-(dimethylamino)-3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 1
- UBDHSURDYAETAL-UHFFFAOYSA-N 8-aminonaphthalene-1,3,6-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 UBDHSURDYAETAL-UHFFFAOYSA-N 0.000 description 1
- 101710025934 ADD3 Proteins 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L Magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- WVMBPWMAQDVZCM-UHFFFAOYSA-N N-methylanthranilic acid Chemical compound CNC1=CC=CC=C1C(O)=O WVMBPWMAQDVZCM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N Triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 241001459538 Ute Species 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 239000011776 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
Definitions
- Thecorripound has-the unique characteristic of;Being'colorlessj'ornearly so, under normal condition's',1'but changes to an intense blue upon being placed in adsorption contact with highly polar substances such" as clay, silicon dioxide, and magnesium carbonate, or when in contact with weak acids. It has, among other utilities, unique value' as an ingredient" of paper-coating compounds which include clay or other dry solid polar-fillers.
- Such coatings when suitably made, as:.. describ'ed in the co-pending application of Barrett-Kt Green 'for United States Letters Patent,-Serial TNo. 581,834,.fi1ed March 5, 1945', now abandoned, respond tomarking pressures by produclnga, color. This novel compound, crystal violetlactone, produces a strong color in such coatings, and. isthighly stable against environmental" actionzin both the. polarized and the unpolarizedstates.
- Crystal violet lactone may be prepared by condensing; Michlers hydrol, having the structure 11 with medimethylaminobenzoic acid, having-the structure 1 Claim. (C1. 260 31443) to p oduce a int rmedia p yi 7- biseiifiethyle en b yqrvu dim ii-- m i 'iqbenzoi t i ,twh p si bse il n l x e to ciy'st'al violet l'actone;" 1
- the m-dimethylai ninohenzoic acid ' may The made by the methyliaat'i'o'n of m aifiinatniic acid, having the structure coin using methyl iodide in the presence of anaqueous solution 10f potas hydroxide.
- the Inaminobenzoic acid is obtainable "comm but at present only'in small amounts?"- It s how ever; a well-known compound.-
- the 'first" stepin the preparation of n-idimethyla'ininohenzoic acid is'to produce its b'e'tain'.
- the -second andithirdi charges are added successively, the timi'nlaof' the third charge, as in the case of the second charge,
- the betain which has the structure
- the leuco-carboxy compound 2-(4,4'-bisdimethylaminobenzohydryl) -5-dimethylaminobenzoic acid having the structure 0:0 (OHzhN mom -HI-Hz0 N(OH:): 00:11
- the tempera- H 0 OH Mom) ture slowly climbs to a point at which the decom- J position is completed.
- the decomposition should be carried on slowly and carefully to prevent loss CH N Nam) of product by entrainment.
- a light oil which is essentially the free betain, remains in the flask.
- the temperature of the oil is then raised to 235 degrees centigrade for approximately fifteen H Hi0 minutes, during which the transition of the betain to the corresponding ester takes place.
- the ester having the formula more As an example, 18 grams of m-dimethylaminobenzoic acid crystals is mixed and powdered with 27 grams of Michlers hydrol.
- the brown acid solution is then poured tion made of 100 milliliters of concentrated hy- Slewly t 1,000 am f ice.
- the dilute acid solution is then partially neutralized, result ng solution is boiled for five minutes to While being stirred with a strong sodium hya q y the T acid Solution of droxide solution, followed by more precise neum -d-1methylam1nobenzo1c acid should be treate tralization accomplished by adding sodium carith activated Charcoal a boiled for a few bonate solution as long as the precipitate, which m nutes longer to decolorize it.
- the TeS1du'a1 a-ctiVated grams of solid hydrated sodium acetate is then charcoa 1 s a hed W a Small qllantlty of hot added, the solution being constantly stirred.
- the water while still on the filter, and the washings resulting mixture is permitted to stand several are addedtothemainfi ltrate. hours in a cool place.
- the cooled mixture is Next, fthylammobenzoic acid is isolated filtered to recover the solid condensation prodfrom the resul g acid solution.
- the acid soluucts which are washed on the filter with water tion of m-dimethylaminobenzoic acid is cooled and thereafter redissolved in a minimum quanand partially neutralized with a cold saturated tit of dilute hydrochloric acid, plut ion of sod um hydroxide.
- the free leuco-carboxy comair-dried product may be further purified by repound-namely, 2-(4,4'-bisdimethylaminobenzocrystallizing it from its solution in hot benzene. hydryl) -5-dimethylaminobenzoic acid --crysta1- lizes out from the acid solution on cooling and standing.
- This leuco-carboxy compound is filtered OE and dried in a desiccator over a drying substance such as Drierite. The dried leucocarboxy compound is re-crystallized from a hot benzene solution.
- Oxidation of the leuco-cwrboxy compound 2-(4.4-bisdimethylaminobenzohydryl) 5 methylaminobeneoic acid One hundred and twelve grams of the dry leuco-carboxy compound is dissolved in 10.7 liters of N/lO hydrochloric acid, and one liter of water is added. Heat may be necessary to complete the solution.
- the resulting solution is cooled to zero degrees centigrade by means of an ice-salt bath, and 72 grams of 90% lead dioxide is added slowiv, with stirring, in the form of a thin past-e.
- the resulting mixture should be stirred for fifteen minutes to complete the oxidation.
- Forty-two grams of anhydrous sodium sulphate dis-solved in one liter of Water is then added to the oxidation mixture to precipitate the lead as sulphate.
- the resulting mixture is then treated with sufiicient hydrochloric acid to just dissolve the crystal violet lactone, which tends to precipitate out in the dilute hydrochloric acid during oxidation.
Description
Reissued Aug. 17, 1948 3,31-BIS l-DIMETHYLAMINOPHENYL) -6- DIMETHYLAMINOPHTHALIDE Clyde S. Adams, Yellow Springs, Ohio, assignor to The National Cash Register Company, ton, Ohio, a corporation of Maryland No Drawing. Original No. 2,417,897, dated March 25, 1947, Serial No. 599,967,,Iune16,1945: 1 1 plication for reissue November 22, fieoial This invention relates to the new compound 3,3 his(4-dimethylaminophenyl) 5 dimethyl aminophthalide', having the structure N (CH3) 2 and which, for purposes, of convenience, will be referred to herein as the lactone of crystal violet or as crystal violet lactone. ,The'novel compoundhas amelting point of approximately 183 degrees centigrade and crystallifies f'rom' ethyl alcohol in long needle-shaped white crystals.
Thecorripound has-the unique characteristic of;Being'colorlessj'ornearly so, under normal condition's',1'but changes to an intense blue upon being placed in adsorption contact with highly polar substances such" as clay, silicon dioxide, and magnesium carbonate, or when in contact with weak acids. It has, among other utilities, unique value' as an ingredient" of paper-coating compounds which include clay or other dry solid polar-fillers. Such coatings, when suitably made, as:.. describ'ed in the co-pending application of Barrett-Kt Green 'for United States Letters Patent,-Serial TNo. 581,834,.fi1ed March 5, 1945', now abandoned, respond tomarking pressures by produclnga, color. This novel compound, crystal violetlactone, produces a strong color in such coatings, and. isthighly stable against environmental" actionzin both the. polarized and the unpolarizedstates.
, -Qther uses forthe novelsubstance will parallel uses-for other known triphenyl methane lact'ones.
Crystal violet lactone may be prepared by condensing; Michlers hydrol, having the structure 11 with medimethylaminobenzoic acid, having-the structure 1 Claim. (C1. 260 31443) to p oduce a int rmedia p yi 7- biseiifiethyle en b yqrvu dim ii-- m i 'iqbenzoi t i ,twh p si bse il n l x e to ciy'st'al violet l'actone;" 1
Michlers' hydrfolfmay be obtained" commercially; as it is'jan' important intermediatef ihfthe dyestufi industifyybiit L n 'rnethymminohe'nzoicacidis not obtainable even for laboratory use) so an ethod of its'preparation"will'fbe'given:
Preparation" of 'moiynetny mgnmqbengoi oeid' The m-dimethylai ninohenzoic acid 'may The made by the methyliaat'i'o'n of m aifiinatniic acid, having the structure coin using methyl iodide in the presence of anaqueous solution 10f potas hydroxide. The Inaminobenzoic acid is obtainable "comm but at present only'in small amounts?"- It s how ever; a well-known compound.- The 'first" stepin the preparation of n-idimethyla'ininohenzoic acid is'to produce its b'e'tain'. Seventy "grains of m'a'minohe'nz'oic' acidisdissdvedWn 700 flask fitted witha 'cork The resultingini' maybe warmed" to 'efiect completesolu'tionf the solution, when cooled," is added 225'gramsof methyl iodide, followed by"the""addition"of r05 grams of. potassium hydroxide; which-is the approximate strength of the ordinary corfinier cial C..P. product, in'threeseparate harges'of 35 grams each, each ss-gr'amcharge'hein'g "pre viously dissolved, in, cc: of. 50 methyl alcohol. The first cha'rgeis:introduced intb the flask, which is stoppered' and permit'tedtd stand at room temperature until'a-"test'showsthat the" solution is acid. The -second andithirdi charges are added successively, the timi'nlaof' the third charge, as in the case of the second charge,
.The contents v of the flask are now subjected to distillation until most 'oi the methyl alcohol-has e ndi l fi f y reme n n j-aque r m 21 jWW mi ute's, weaned l-l1--' liters of 50% methyl-alcohol, using atwo 4 hydrochloric acid (37% gas content by weight) Condensation of Michlers hydrol with m-dimethis added. On standing and cooling, white crysylaminobenzoic acid tals of the hydrated hydriodic acid salt of m-trimethylbenzbetain separate out. These crystals are filtered on and air dried. 5
The betain, which has the structure The leuco-carboxy compound 2-(4,4'-bisdimethylaminobenzohydryl) -5-dimethylaminobenzoic acid, having the structure 0:0 (OHzhN mom -HI-Hz0 N(OH:): 00:11
is next converted to the methyl ester of m-dimethylaminobenzoic acid in the following man- N 9: ner. Enough of the betain prepared in accordis prepared by condensing Michlers hydrol with ance with the preceding step to make 100 gr m-dimethylaminobenzoic acid, said condensation 1s placed in a wide-mouthed Erlenmeyer flask being represented as f ll w immersed in an oil bath. The temperature is 00 H gradually raised to a point at which the betain (CHWN begins to melt and decompose, giving ofi gaseous HISOI hydrogen iodide and water vapor. The tempera- H 0 OH Mom) ture slowly climbs to a point at which the decom- J position is completed. The decomposition should be carried on slowly and carefully to prevent loss CH N Nam) of product by entrainment. A light oil, which is essentially the free betain, remains in the flask. The temperature of the oil is then raised to 235 degrees centigrade for approximately fifteen H Hi0 minutes, during which the transition of the betain to the corresponding ester takes place. The ester, having the formula more As an example, 18 grams of m-dimethylaminobenzoic acid crystals is mixed and powdered with 27 grams of Michlers hydrol. The resulting in- N(CH3)I timate mixture is then added very slowly to 212 grams of 90% sulphuric acid which has been preis then cooled and solidifies into a wax-like solid. gg ff rfifig gfi gfiig 22 g gz figfifilg stfiggs The ester p e in e Precedmg e 18 during the addition of the mixture. After addith n Sflponlfied 1n the following manner- W' 5 tion of the mixture, the resulting solution is alf ms of the waxy methy ester of lowed to stand at room temperature for several methylaminobenzoic acid is dissolved in a soluhours. The brown acid solution is then poured tion made of 100 milliliters of concentrated hy- Slewly t 1,000 am f ice. The resulting drochlo c d a d 100 {mlhhters of Water- The dilute acid solution is then partially neutralized, result ng solution is boiled for five minutes to While being stirred with a strong sodium hya q y the T acid Solution of droxide solution, followed by more precise neum -d-1methylam1nobenzo1c acid should be treate tralization accomplished by adding sodium carith activated Charcoal a boiled for a few bonate solution as long as the precipitate, which m nutes longer to decolorize it. The resulting fir t forms,redissolves on tirring, Two hundred mixture S fi d Q The TeS1du'a1 a-ctiVated grams of solid hydrated sodium acetate is then charcoa 1 s a hed W a Small qllantlty of hot added, the solution being constantly stirred. The water while still on the filter, and the washings resulting mixture is permitted to stand several are addedtothemainfi ltrate. hours in a cool place. The cooled mixture is Next, fthylammobenzoic acid is isolated filtered to recover the solid condensation prodfrom the resul g acid solution. The acid soluucts, which are washed on the filter with water tion of m-dimethylaminobenzoic acid is cooled and thereafter redissolved in a minimum quanand partially neutralized with a cold saturated tit of dilute hydrochloric acid, plut ion of sod um hydroxide. Final neutraIi a The resulting dilute hydrochloric acid solution tion s accomplished by addl g so carbonate of the condensation products is neutralized with so ut on as lo a the p p w ch fi t a sodium hydroxide solution, excess being added f rm i lv s on sti ri The r s l i g to make the solution definitely alkaline The alsolution is then treated with a saturated solution kaline solution should be boiled for a few minutes o 5011111111 acetate P p d y d s v g 60 gra s cooled, and filtered. The alkaline filtrate con: of hydrated sodium acetate in 50 milliliters of taining the sodium salt of 2-(4,4'-bisdimethyl- Wat he resultmg mixture is allowed to c001,. aminobenzohydryl) -5-dimethy1aminobenz0ic acid and the resulting crystals of m-dimethylaminois acidified with acetic acid, care being taken not benzoic acid are filtered off, washed with a small to add much excess acetic acid after the solution quant ty of cold water, and air dried. This crude becomes acid. The free leuco-carboxy comair-dried product may be further purified by repound-namely, 2-(4,4'-bisdimethylaminobenzocrystallizing it from its solution in hot benzene. hydryl) -5-dimethylaminobenzoic acid --crysta1- lizes out from the acid solution on cooling and standing. This leuco-carboxy compound is filtered OE and dried in a desiccator over a drying substance such as Drierite. The dried leucocarboxy compound is re-crystallized from a hot benzene solution. The resulting gray crystals of 2 (4,4 hisdtmethylaminobenzohydryl) 5 -dimethylarninobenzoic acid, having a melting point of 199-200 degrees centigrade, are filtered off, washed with petroleum ether, and air dried.
Oxidation of the leuco-cwrboxy compound 2-(4.4-bisdimethylaminobenzohydryl) 5 methylaminobeneoic acid One hundred and twelve grams of the dry leuco-carboxy compound is dissolved in 10.7 liters of N/lO hydrochloric acid, and one liter of water is added. Heat may be necessary to complete the solution.
The resulting solution is cooled to zero degrees centigrade by means of an ice-salt bath, and 72 grams of 90% lead dioxide is added slowiv, with stirring, in the form of a thin past-e. The resulting mixture should be stirred for fifteen minutes to complete the oxidation. Forty-two grams of anhydrous sodium sulphate dis-solved in one liter of Water is then added to the oxidation mixture to precipitate the lead as sulphate. The resulting mixture is then treated with sufiicient hydrochloric acid to just dissolve the crystal violet lactone, which tends to precipitate out in the dilute hydrochloric acid during oxidation. The mixture is filtered to remove the lead sulphate, and the filtrate is neutralized with sodium hydroxide solution, making the solution distinctly alkaline. The crystal violet lactone which precipitates out from the alkaline solution is filtered off, washed with a small quantity of cold water, and redissolved in hot 95% ethyl alcohol. If the alcohol solution of the crystal violet lactone ture oHmN N(CH5):
CLYDE S. ADAMS.
REFERENCES CITED The following references are of record in the file of this patent:
I UNITED STATES PATENTS Number Name Date 2,130,430 Austin Sept. 20, 1938 OTHER REFERENCES Chemical Abstracts 32 (1938), page 2106, citing Schwarzengach et al.
Helv. Chem. Acta, 20 (1937), pages 159-1600.
Rec. Trav. Chem., vol. 46, pages 653-98 (page 657) (1927).
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USRE23024E true USRE23024E (en) | 1948-08-17 |
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2742483A (en) * | 1954-06-14 | 1956-04-17 | Sterling Drug Inc | Process for obtaining crystal violet lactone |
US3431282A (en) * | 1963-07-17 | 1969-03-04 | Kanazaki Paper Mfg Co Ltd | Phthalide compounds |
US4399291A (en) | 1981-12-09 | 1983-08-16 | Sterling Drug Inc. | Process for the production of substituted aminophthalides |
US4528136A (en) | 1981-12-09 | 1985-07-09 | The Hilton-Davis Chemical Co. | Process for preparing 2-[bis(aryl)methyl]benzoic acids |
US4927802A (en) | 1988-12-09 | 1990-05-22 | Ppg Industries, Inc. | Pressure-sensitive multi-part record unit |
EP0688759A1 (en) | 1994-06-23 | 1995-12-27 | Fuji Photo Film Co., Ltd. | Alpha-resorcylic acid ester derivatives and recording materials incorporating them |
EP1275519A1 (en) | 2001-06-26 | 2003-01-15 | Fuji Photo Film Co., Ltd. | Recording material |
EP1297966A2 (en) | 2001-09-27 | 2003-04-02 | Fuji Photo Film Co., Ltd. | Heat sensitive recording material |
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0
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US4528136A (en) | 1981-12-09 | 1985-07-09 | The Hilton-Davis Chemical Co. | Process for preparing 2-[bis(aryl)methyl]benzoic acids |
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EP1275519A1 (en) | 2001-06-26 | 2003-01-15 | Fuji Photo Film Co., Ltd. | Recording material |
EP1297966A2 (en) | 2001-09-27 | 2003-04-02 | Fuji Photo Film Co., Ltd. | Heat sensitive recording material |
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WO2004030921A2 (en) | 2002-10-02 | 2004-04-15 | General Data Company, Inc. | Direct thermal imaging on plastic film john finger |
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US20060063125A1 (en) * | 2003-04-22 | 2006-03-23 | Hamilton Timothy F | Method and device for enhanced dental articulation |
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