US2659727A - T kt xtt - Google Patents
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- US2659727A US2659727A US2659727DA US2659727A US 2659727 A US2659727 A US 2659727A US 2659727D A US2659727D A US 2659727DA US 2659727 A US2659727 A US 2659727A
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- amino
- leuco
- ester
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- 150000002148 esters Chemical class 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 18
- XOGPDSATLSAZEK-UHFFFAOYSA-N 2-Aminoanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 XOGPDSATLSAZEK-UHFFFAOYSA-N 0.000 claims description 16
- -1 AMINO GROUP Chemical group 0.000 claims description 14
- UHOKSCJSTAHBSO-UHFFFAOYSA-N Indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 claims description 12
- 235000019239 indanthrene blue RS Nutrition 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 30
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XGBDPAYTQGQHEW-UHFFFAOYSA-N Ferrate(VI) Chemical compound [O-][Fe]([O-])(=O)=O XGBDPAYTQGQHEW-UHFFFAOYSA-N 0.000 description 10
- 125000003277 amino group Chemical group 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000001103 potassium chloride Substances 0.000 description 10
- 235000011164 potassium chloride Nutrition 0.000 description 10
- 159000000001 potassium salts Chemical class 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N Sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- JFTTYFWNHKVEMY-UHFFFAOYSA-N Barium ferrate Chemical compound [Ba+2].[O-][Fe]([O-])(=O)=O JFTTYFWNHKVEMY-UHFFFAOYSA-N 0.000 description 6
- UGCDBQWJXSAYIL-UHFFFAOYSA-N VAT BLUE 6 Chemical compound O=C1C2=CC=CC=C2C(=O)C(C=C2Cl)=C1C1=C2NC2=C(C(=O)C=3C(=CC=CC=3)C3=O)C3=CC(Cl)=C2N1 UGCDBQWJXSAYIL-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910052803 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VMOJFUJVEWWUAV-UHFFFAOYSA-N 2-amino-3-chloroanthracene-9,10-dione Chemical group O=C1C2=CC=CC=C2C(=O)C2=C1C=C(N)C(Cl)=C2 VMOJFUJVEWWUAV-UHFFFAOYSA-N 0.000 description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L Barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N Silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- 229910001626 barium chloride Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- WHWYFOIYRCTLFZ-UHFFFAOYSA-N cobalt;trihydrate Chemical compound O.O.O.[Co] WHWYFOIYRCTLFZ-UHFFFAOYSA-N 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- MSNWSDPPULHLDL-UHFFFAOYSA-K iron(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 4
- 230000001590 oxidative Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-Benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- CLWMYQQCXBSIBF-UHFFFAOYSA-N 2-amino-3-bromoanthracene-9,10-dione Chemical group O=C1C2=CC=CC=C2C(=O)C2=C1C=C(N)C(Br)=C2 CLWMYQQCXBSIBF-UHFFFAOYSA-N 0.000 description 2
- NWBQSTLSGBGAKG-UHFFFAOYSA-N 2-amino-3-methoxyanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(OC)C(N)=C2 NWBQSTLSGBGAKG-UHFFFAOYSA-N 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L Cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N Hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L Nickel(II) chloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N carbodiimide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 230000000737 periodic Effects 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000001187 sodium carbonate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
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
- C09B9/00—Esters or ester-salts of leuco compounds of vat dyestuffs
- C09B9/02—Esters or ester-salts of leuco compounds of vat dyestuffs of anthracene dyes
Definitions
- This invention relates to an improved process of preparing leuco indanthrone tetrasulfuric esters by the oxidative condensation of leuco betaaminoanthraquinone disulfuric esters.
- the cost of the lead is so high that such as acetylamino and sulfamido compounds no process using it as an oxidizing agent can be may be empl y and throughout the specification carried out without recovery of lead, which preand claims the term a beta-aminoanthraqui-
- the drawbacks to the none includes the beta-acyl amino anthraquilead dioxide process are sufiiciently serious so nones as well as those having a free amino group.
- reaction mixture is held at 85 until oxidation is complete, filtered, concentrated to 80 parts by volume, and salted with 20 parts of potassium chloride. After thorough stirring and cooling. the product is filtered. A good yield of the tetrasulfuric acid ester of the dichloro leuco indanthrone is obtained.
- Example 2 Barium ferrate is prepared by adding a solution of 13.5 parts of ferric chloride in 20 parts of water to a solution of 20 parts of potassium hydroxide in 50 parts of water. To the resulting ferric hydroxide precipitate is added 100 parts by volume of 15% sodium hypochlorite solution, giving a violet solution, which is heated briefly at 80 C. To this is added a solution of 13 parts of barium chloride in 50 parts of water. The purple precipitate which forms immediately is filtered and washed.
- the barium ferrate, prepared as described, is added to a batch of 2-amino-3-chloro-anthrahydroquinone-disulfurio ester, prepared as described in Example 1.
- the oxidation is carried out at 60 C.
- the mixture is filtered, concentrated to 50 parts by volume, salted at 60 C. with 7 parts of potassium chloride and 20 parts of methanol, and cooled thoroughly. On filtration, there is obtained a good yield of the yelloworange potassium salt of the leuco dichloro indanthrone tetrasulfuric ester.
- Example 3 An aqueous solution of 12.5 parts of nickel chloride and 10 parts of sodium carbonate is oxidized by treatment with 100 parts by volume of 10% sodium hypochlorite solution. The resulting nickel dioxide is added to a batch of 2- amino-3-chloroanthrahydroquinone disulfuric ester prepared as described in Example 1. Oxidation is completed at 85 C. The reaction mixture is filtered, concentrated to 50 parts by volume, and salted with parts of potassium chloride followed by 12 parts of methanol. After thorough stirring, filtration gives a good yield of the light orange potassium salt of the leuco dichloro indanthrone tetrasulfuric ester.
- Example 4 A mixture of 20.0 parts of the potassium salt of 2-acetylamino-3-bromo anthrahydroquinone- 9,10-disulfuric acid ester, 14 parts sodium hydroxide, and 120 parts of water is stirred at 85
- Example 5 An aqueous solution containing the ferrate ion is prepared by adding a solution of 27 parts of ferric chloride in 100 parts of water to a solution of 40 parts of potassium hydroxide in 50 parts of water. To the resulting ferric hydroxide precipitate is added at 70, 100 parts by volume of 15% sodium hypochlorite solution. After stirring and heating at the mixture is filtered and a violet solution is obtained.
- This violet solution containing the ferrate ion, is added to a batch of 2-amino-3-chloro-anthrahydroquinone-disulfuric ester prepared as described in Example 1. After carrying out the oxidation at 60, the excess ferrate is removed by precipitation with barium chloride. The mixture is then filtered. concentrated to 60 parts by volume, salted at 60 with 12 parts of potassium chloride and 30 parts of methanol, and cooled thoroughly. On filtration, the potassium salt of the leuco dichloroindanthrone tetrasulfuric ester is obtained in good yield.
- Process of preparing a leuco indanthrone tetrasulfuric ester which comprises reacting the leuco sulfuric ester of a beta-aminoanthraquinone having a free position alpha to the amino group with compound of nickel having a valence of at least 3 and not more than 4.
- a process of preparing leuco indanthrone tetrasulfuric esters which comprises reacting a leuco sulfuric ester of a beta-aminoanthraquinone with a free position alpha to the amino group with a compound of cobalt having a valence of 3.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Nov. 17, 1953 UNITED STATES PREPARATION OF LEUCO-INDANTHRONE SULFURIC ESTERS William B. Hardy, Bound Brook, and Robert B; Fortenbaugh, Gladstone, N. J., assignors to American Cyanamid Company, New York, N. Y.,
a corporation of Maine No Drawing. Application February 15, 1952, 'Serial No. 271,868
This invention relates to an improved process of preparing leuco indanthrone tetrasulfuric esters by the oxidative condensation of leuco betaaminoanthraquinone disulfuric esters.
actions.
drawbacks.
sents serious problems.
in spite of its high cost.
of oxidation.
compounds.
metals.
diners.
any theoretical explanation.
cal.
16 Claims. (Cl. 260-265) spent oxidizing agent readily and substantially quantitatively by filtration and; if desired, it can be regenerated and reused. The product is obtained in the filtrate from which it can be isolated in good yields and satisfactory purity by beta-aminoanthraquinone,
3 bromo-2- and These include barium The invention, of course,
In the past, the production of leuco indan- 5 throne tetrasulfuric esters has been attempted conventional means. with various oxidizing agents, such as ferricy- The present invention is applicable generally to anides, hypochlorites and lead dioxide, which are leuco sulfuric esters of beta-aminoanthraquiusable under alkaline conditions. These pronones, the only requirement of course being that cedures have been subject to undesirable side rethere be a free alpha p t n a ja ent t the These have been particularly serious amino group. Typical esters which may be used with the alkali metal ferricyanides and hypochloare the following: rites; and as a result the only process which has B-chloro -2- aminoanthraquinone, had any practical significance is one using lead aminoanthraquinone, 2-aminoanthraquinone-3- dioxide under alkaline conditions as the oxidizcarboxylic acid, 2-amino-3-methyl anthraquiing agent. While this process has been sufiiciently none, 2-amino-3-methoxyanthraquinone; effective to be used for actual practical produccompounds containing condensed rings, such as tion of the esters, it suffers from a number of 1,2-benz-3-aminoanthraq are also Suitable- Lead is expensive and its high mo- Esters may be used in the form of the amino comlecular weight makes it a very wasteful oxidizp nds r. f ir eir N- y riv v ing agent. The cost of the lead is so high that such as acetylamino and sulfamido compounds no process using it as an oxidizing agent can be may be empl y and throughout the specification carried out without recovery of lead, which preand claims the term a beta-aminoanthraqui- The drawbacks to the none includes the beta-acyl amino anthraquilead dioxide process are sufiiciently serious so nones as well as those having a free amino group. that it has even been proposed to use silver oxide While the i p oved r u t f t e p nt invention are obtainable with any compounds of According to the present invention, we have the metals of group VIII in their higher state of found that if simple compounds, not complexes, oxidation, certain specific compounds of this class of the metals of group VIII of the periodic sysare readily obtainable and are, therefore, prefertern, having atomic numbers 26, 2'7 and 28, i. e., able for economic reasons. iron, cobalt and nickel, are used as oxidizing and strontium perferrites, alkali and alkaline agents, the reaction proceeds smoothly and no earth metal ferrates, such as ferrates of sodiniculty is encountered. However, in order to dium, potassium, calcium and barium; cobaltic be oxidizing agents for practical purposes, in these hydroxides, cobaltic dioxide and oxides of tricompounds the metal must be in a higher state and tetravalent nickel.
In the case of iron, the valence is not limited to the use of these preferred oximust be l or 6, trivalent ferric iron will not opdizing agents. erate satisfactorily. Cobalt in the tri and tetra- The invention will be described in greater devalent state and nickel in the tri and tetravalent tail in conjunction with the following specific state may also be used in the form of their simple examples, the parts being by weight unless other- Not only do the oxidizers of the Wise indicated. present invention operate smoothly and efficiently, but their low molecular weight improves output. Example 1 It is not known why the improved results are so specific to the higher oxidation state of the three A mlxtur? of parts of the potassium salt of Ordinarily, Complex trivalent iron Z-acetylammo chloro-anthrahydroquinonepounds such as ferricyanides are powerfulpoxi- F f acld ester 4 P sodium Yet in the present process, they do not dioxide, and 35 parts of water is stlrred at 85 till give useful'results, whereas tetravalent and hex- 60 1137913157518 Ofthe acetyl group is complete as indi' malem iron cgmpounds can be used Very efiec catedby the failure of any precipitate to form tively. We do not know Why th 'higher t t w en a drop of the reaction solution is diluted oi oxidation give the improved results and it is with 2 9 Water and treated with a few crys' i t n j d to limit the present invention to tals of sodium nitrite followed by dilute hydro- ChlOIiC acid. it is an advantage of the present invention To the hydrolyzed solution containing the dithat the reaction conditions are in no sense criti- Sulfuric ester of 2amino'3-ch101'anthmhydr0 The reactmn prgceeds readily in aqueous quinone, is added 5.5 parts of cobaltic hydroxide medium at moderate temperatures, preferably Prepared y a g -5 p ts of cobaltous acetate slightly above room temperature. When the reto a solution of 10 parts of potassium hydroxide in action is complete, it is possible to recover the parts by volume of 15% sodium hypochlorite solution, filtering and washing the resulting black precipitate.
The reaction mixture is held at 85 until oxidation is complete, filtered, concentrated to 80 parts by volume, and salted with 20 parts of potassium chloride. After thorough stirring and cooling. the product is filtered. A good yield of the tetrasulfuric acid ester of the dichloro leuco indanthrone is obtained.
Example 2 Barium ferrate is prepared by adding a solution of 13.5 parts of ferric chloride in 20 parts of water to a solution of 20 parts of potassium hydroxide in 50 parts of water. To the resulting ferric hydroxide precipitate is added 100 parts by volume of 15% sodium hypochlorite solution, giving a violet solution, which is heated briefly at 80 C. To this is added a solution of 13 parts of barium chloride in 50 parts of water. The purple precipitate which forms immediately is filtered and washed.
The barium ferrate, prepared as described, is added to a batch of 2-amino-3-chloro-anthrahydroquinone-disulfurio ester, prepared as described in Example 1. The oxidation is carried out at 60 C. There is then added 5 parts of potassium chloride. The mixture is filtered, concentrated to 50 parts by volume, salted at 60 C. with 7 parts of potassium chloride and 20 parts of methanol, and cooled thoroughly. On filtration, there is obtained a good yield of the yelloworange potassium salt of the leuco dichloro indanthrone tetrasulfuric ester.
Example 3 An aqueous solution of 12.5 parts of nickel chloride and 10 parts of sodium carbonate is oxidized by treatment with 100 parts by volume of 10% sodium hypochlorite solution. The resulting nickel dioxide is added to a batch of 2- amino-3-chloroanthrahydroquinone disulfuric ester prepared as described in Example 1. Oxidation is completed at 85 C. The reaction mixture is filtered, concentrated to 50 parts by volume, and salted with parts of potassium chloride followed by 12 parts of methanol. After thorough stirring, filtration gives a good yield of the light orange potassium salt of the leuco dichloro indanthrone tetrasulfuric ester.
Example 4 A mixture of 20.0 parts of the potassium salt of 2-acetylamino-3-bromo anthrahydroquinone- 9,10-disulfuric acid ester, 14 parts sodium hydroxide, and 120 parts of water is stirred at 85 Example 5 An aqueous solution containing the ferrate ion is prepared by adding a solution of 27 parts of ferric chloride in 100 parts of water to a solution of 40 parts of potassium hydroxide in 50 parts of water. To the resulting ferric hydroxide precipitate is added at 70, 100 parts by volume of 15% sodium hypochlorite solution. After stirring and heating at the mixture is filtered and a violet solution is obtained.
This violet solution, containing the ferrate ion, is added to a batch of 2-amino-3-chloro-anthrahydroquinone-disulfuric ester prepared as described in Example 1. After carrying out the oxidation at 60, the excess ferrate is removed by precipitation with barium chloride. The mixture is then filtered. concentrated to 60 parts by volume, salted at 60 with 12 parts of potassium chloride and 30 parts of methanol, and cooled thoroughly. On filtration, the potassium salt of the leuco dichloroindanthrone tetrasulfuric ester is obtained in good yield.
We claim:
1. Process of preparing leuco indanthrone tetrasulfuric esters which com rises reacting a leuco sulfuric ester of a beta-amino-anthra quinone having a free position alpha to the amino group with a compound containing as an anion iron having an even valence not less than 4 and not greater than 6.
2. Process according to claim 1 in which the iron compound is a ferrate.
3. Process according to claim 2 in which the beta-arninoanthraquinone is 2-arnino-3-halogenanthraquinone.
4. Process according to claim 3 in which the 2-amino-3-halogenanthraquinone is 2-ami11of5--chloroanthraquinone.
5. Process according to claim 4 in which the ferrate is an alkali metal ferrate.
6. Process according to claim 3 in which the ferrate is an alkaline earth metal ferrate.
'7. Process according to claim 6 in which the ferrate is barium ferrate.
8. Process of preparing a leuco indanthrone tetrasulfuric ester which comprises reacting the leuco sulfuric ester of a beta-aminoanthraquinone having a free position alpha to the amino group with compound of nickel having a valence of at least 3 and not more than 4.
9. Process according to claim 8 in which the nickel compound is nickel dioxide.
10. Process according to claim 9 in which the beta-aminoanthraquinone is 2-amino-3-halogenanthraquinone.
11. Process according to claim 10 in which the 2-amino-3-halogenanthraquinone is 2-amino-3- chloroanthraquinone.
12. Process according to claim 10 in which the 2-amino-3-halogenanthraquinone is 2-amino-3- bromoanthraquinone.
13. A process of preparing leuco indanthrone tetrasulfuric esters which comprises reacting a leuco sulfuric ester of a beta-aminoanthraquinone with a free position alpha to the amino group with a compound of cobalt having a valence of 3.
14. A process according to claim 13 in which the cobalt compound is cobaltic hydroxide.
15. A' process according to claim 14 in which the leuco sulfuric ester is of a 2-amino-3-halogenanthraquinone.
16. A process according to claim 15 in which the 2-amino3halogenanthraquinone is 2-amino-3-chloroanthraquinone.
WILLIAM B. HARDY. ROBERT E. FORTENBAUGH.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,344,389 Bretagne et al Mar. 14, 1944
Claims (1)
1. PROCESS OF PREPARING LEUCO INDANTHRONE TETRASULFURIC ESTERS WHICH COMPRISES REACTING A LENCO SULFURIC ESTER OF A BETA-AMINO-ANTHRAQUINONE HAVING A FREE POSITION ALPHA TO THE AMINO GROUP WITH A COMPOUND CONTAINING AS AN ANION IRON HAVING AN EVEN VALENCE NOT LESS THAN 4 AND NOT GREATER THAN 6.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2659727A true US2659727A (en) | 1953-11-17 |
Family
ID=3439978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2659727D Expired - Lifetime US2659727A (en) | T kt xtt |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2659727A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2344389A (en) * | 1944-03-14 | Process foe the preparation of dye |
-
0
- US US2659727D patent/US2659727A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2344389A (en) * | 1944-03-14 | Process foe the preparation of dye |
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