US506265A - Robert e - Google Patents
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- US506265A US506265A US506265DA US506265A US 506265 A US506265 A US 506265A US 506265D A US506265D A US 506265DA US 506265 A US506265 A US 506265A
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- alizarin
- hexacyanin
- pentacyanin
- sulfuric acid
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- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 102
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 102
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 66
- 239000000243 solution Substances 0.000 description 40
- 239000000203 mixture Substances 0.000 description 32
- VBHKTXLEJZIDJF-UHFFFAOYSA-N Quinalizarin Chemical compound C1=CC(O)=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1O VBHKTXLEJZIDJF-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical compound [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 16
- 230000001590 oxidative Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-Benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N Nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- VOTFXKJPNQELOG-UHFFFAOYSA-N arsenic acid Chemical compound O[As](=O)=O VOTFXKJPNQELOG-UHFFFAOYSA-N 0.000 description 10
- 229940000488 arsenic acid Drugs 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 229960000583 Acetic Acid Drugs 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 238000004043 dyeing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000004345 1,2-dihydroxyanthraquinones Chemical class 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- WNHUAWNEKMITEW-UHFFFAOYSA-N Anthrapurpurin Chemical compound C1=C(O)C(O)=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1 WNHUAWNEKMITEW-UHFFFAOYSA-N 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L Sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 6
- 150000004053 quinones Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000001187 sodium carbonate Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- BBNQQADTFFCFGB-UHFFFAOYSA-N 1,2,4-Trihydroxyanthraquinone Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC(O)=C3C(=O)C2=C1 BBNQQADTFFCFGB-UHFFFAOYSA-N 0.000 description 4
- 241000974482 Aricia saepiolus Species 0.000 description 4
- RDFLLVCQYHQOBU-GPGGJFNDSA-O Cyanin Natural products O([C@H]1[C@H](O)[C@H](O)[C@H](O)[C@H](CO)O1)c1c(-c2cc(O)c(O)cc2)[o+]c2c(c(O[C@H]3[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O3)cc(O)c2)c1 RDFLLVCQYHQOBU-GPGGJFNDSA-O 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N Sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 210000002268 Wool Anatomy 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M CHEMBL593252 Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- ASCUXPQGEXGEMJ-GPLGTHOPSA-N [(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-[[(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-(4-methylanilino)oxan-2-yl]methoxy]oxan-2-yl]methyl acetate Chemical compound CC(=O)O[C@@H]1[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H](COC(=O)C)O[C@@H]1OC[C@@H]1[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](NC=2C=CC(C)=CC=2)O1 ASCUXPQGEXGEMJ-GPLGTHOPSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KNCZUXHSQJQWIB-UHFFFAOYSA-N anthracene-1,4,9,10-tetrone Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(=O)C=CC2=O KNCZUXHSQJQWIB-UHFFFAOYSA-N 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical class [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000003467 diminishing Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003638 reducing agent Substances 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
- 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
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- UPKAWFACSJWKND-ZXFFUEEESA-J tetrasodium;(6E)-4-amino-6-[[4-[4-[(2Z)-2-(8-amino-1-oxo-5,7-disulfonatonaphthalen-2-ylidene)hydrazinyl]-3-methoxyphenyl]-2-methoxyphenyl]hydrazinylidene]-5-oxonaphthalene-1,3-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C\1=CC2=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C(N)=C2C(=O)C/1=N/NC(C(OC)=C1)=CC=C1C1=CC=C(N\N=C\2C(C3=C(N)C(=CC(=C3C=C/2)S([O-])(=O)=O)S([O-])(=O)=O)=O)C(OC)=C1 UPKAWFACSJWKND-ZXFFUEEESA-J 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
Definitions
- alizarin bordeaux which I haveobtained by oxidizing alizarin with a large excess of sulfuric anhydride in the form of a strong fuming sulfuric acid at a low temperature.
- My new invention relates to the production of a new coloring-matter byfurther oxidizing the said alizarin pentacyaniu a dye-stud being thus formed which is a hexaoxyanthraquinone and which I briefly term alizarin hexacyanin. It is difierent from the alizarin pentacyanin by its composition and properties, from the isomeric hexaoxyanthraquinone which I have described and claimed in a separate application and which I briefly term hexaoxyanthraquinone it chiefly differs by its dyeing properties.
- the coloring-matter separating is filtered off and washed out.
- the latter is redissolved in the necessary quantity of soda-lye and the alkaline solution after having been filtered is decomposed by the addition of acids.
- the product precipitated is a mixture of alizarin hexacyanin and hexaoxyanthraquinone, as above mentioned.
- the mixture is crystallized at first out of nitrobenzene, then repeatedly out of alco- 1101, in which the hexaoxyanthraquinone is more difficultly soluble than alizarin hexacyanin.
- alizarin pentacyanin is produced by oxidizing alizarin bordeaux, it is not necessary to start from alizarin pentacyanin but alizarin bordeaux may be employed without isolating the alizarin pentacyanin produced as an intermediate product.
- alizarin bordeaux into alizarin hex acyanin: Ten parts, by weight, of dry alizarin bordeaux are dissolved in two hundred parts, by weight, of concentrated sulfuric acid at 66 Baum and fifteen parts, by weight, of finely pulverized manganese dioxid (containing ninety per cent. of dioxid) are gradually introduced, the temperature being kept at from 50 to 55 centigrade.
- the gradual conversion of alizarin bordeaux into alizarin pentacyanin and alizarin hexacyanin isto be recognized very distinctly by the usual spectroscopic examination. When the spectrum of the pentacyanin has totally disappeared the sulfuric acid liquid is treated in the same manner as described in the preceding example.
- alizarin hexacyanin by oxidizing alizarin bordeaux by means of arsenic acid: A mixture of ten parts, by weight, of alizarin bordeaux, two hundred parts, by weight, of sulfuric acid at 66 Baum and fifteen parts, by weight, of dry arsenic acid are heated for about six hours at a temperature from 140 to 150 centigrade and the resulting mixture then is poured into water. By filtering off, redissolving in alkali and precipitating again with acids, separating the two products formed in the manner before described the alizarin hexacyanin dye-stuif is isolated.
- alizarin hexacyanin In order to produce alizarin hexacyanin by treating alizarin pentacyanin with concentrated sulfuric acid at higher temperatures I proceed as follows: Ten parts, by weight, of alizarin pentacyanin and two hundred parts, by weight, of sulfuric acid at 66 Baum are heated at centigrade until a sample of the mixture diluted with sulfuric acid shows no more the spectrum of alizarin pentacyanin. When the latter has been found to be totally converted the whole liquid is poured into water and the coloring matter separated by fil tering off, washing out and isolated in the manner above described.
- Anthrapurpurin is converted into pure alizarin hexacyanin by an energetic oxidation with the aid of manganese dioxid.
- oxyanthrapurpurin which is a coloring-matter dyeing a yellowishred on cotton mordanted with alumina salts, but possesses only an inferior value for dyeing purposes.
- the oxyanthrapurpurin is transformed into the quinone of alizarin hexacyanin and this quinone, is then converted into the cyanin (alizarin hexacyanin) by a subsequent treatment with reducing agents employing most practically sulfurous acid.
- a pulverized mixture containing ten parts, by weight, of anthrapurpurin and nineteen parts, by weight, of manganese dioxid (ninety per cent.) is introduced with constant agitation into three hundred parts, by weight, of sulfuric acid at 66 Baum taking care that the temperature does not rise above 35 centigrade. After the whole manganese dioxid has been added, the mixture is allowed to stand for half an hour. Then it is poured into three thousand parts, by weight, of water mixed with ten parts, by weight, of an aqueous solution of sodium bisul fit at 55 Baum. The liquid is heated to the boiling point and the coloringinatter separated is filtered off, washed out and purified by redissolving, dad, in the well known manner.
- alizarin hexacyanin is insoluble in water and very moderately soluble in alcohol with dark rose-red color and in glacial acetic acid with a more yellowish-red color both solutions showing a yellowish-bro wn fluorescence.
- Alcohol or glacial acetic acid it separates in dark brilliant crystals. It is easily soluble in boiling nitrobenzene and very easily in pyridin.
- alkaline solutions are decomposed by adding acids or on pouring its solution in concentrated sulfuric acid into water it separates in reddish-brown flakes which after filtering off yield a dark brown paste that is most fit for dyeing and printing purposes.
- Hexaoxyanthraquinone dissolves in a solution of. sodium carbonate with bluish-red, in sodalye with violet color which gradually turns into blue in the air blue flakes being further separated after some time, in ammonia liquid with bluish-red color which changes into violet in the air, in pure concentrated sulfuric acid with bluish-violet color which turns into yellowish-red on adding water, yellowish-brown flakes being separated after some time.
- alizarin derivatives further differ by the absorption spectra of their sulfuric acid solutions.
- Alizarin hexacyanin displays two strong absorption bands, the one in the red part and the other in the green part of the spectrum, while hexaoxyanthraquinone shows one strong absorption bandin the orange part and a slighter one in the yellowish-green part of the spectrum.
- the shades produced by alizarin hexacyanin on wool mordanted with chromium or alumina salts are in general more greenish than those obtained by employing hexaoxyanthraquinone. It produces on wool mor-' danted with alumina salts violet, on W001 mordanted with chromium salts blue shades both being more greenish than those resulting from the alizarin pentacyanin and hexaoxyanthraquinone which I have described in separate specifications.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
INITED STATES PATENT .OFFICE.
ROBERT E. SCHMIDT, OF ELBERE ELD, GERMANY, ASSIGNOR TO THE FARBENFABRIKEN, VORMALS FR. BAYER & CO., OF SAME PLACE.
ALIZARINHEXACYANIN.
SPECIFICATION forming part of Letters Patent No. 506,265, dated October 10, 1893. Application filed May 11, 1892. Serial No. 432,611. ($pecimens.) Patented in England March 12,1892, N0- 4,8'71.
To all whom, it may concern:
Be it known that I, ROBERT E. SCHMIDT, doctor of philosophy and chemist, (assignor to the FARBENFABRIKEN, VORMALS FR. BAYER & 00., of Elberfeld,) a subject of theEmperor of Germany, residing'at Elberfeld, Germany, have. invented a new and useful Improvement in the Manufacture of Alizarin Derivatives, (for which the aforesaid FARBENFABRIKEN have already obtained Letters Patent in England, No. 4,871, dated March 12, 1892,) of which the following is a clear and exact description.
I have described in the United States Letters Patent No. 446,893, dated February 24, 1891, the production of an alizarin derivative called alizarin bordeaux which I haveobtained by oxidizing alizarin with a large excess of sulfuric anhydride in the form of a strong fuming sulfuric acid at a low temperature.
In the United States Letters Patent No. 446,892, dated February 24, 1891, I have described another valuable alizarin dye-stuff which is produced by oxidizing the aforesaid alizarin bordeaux in sulfuric acid solution with manganese dioxid. While the alizarin bordeaux is a tetraoxyanthraquin'one the product resulting from alizarin bordeaux by further oxidation represents a pentaoxyanthraquinone. In order to express the constitution and the cyanine like character of this latter product I briefly term it alizarin pentacyanin.
My new invention relates to the production of a new coloring-matter byfurther oxidizing the said alizarin pentacyaniu a dye-stud being thus formed which is a hexaoxyanthraquinone and which I briefly term alizarin hexacyanin. It is difierent from the alizarin pentacyanin by its composition and properties, from the isomeric hexaoxyanthraquinone which I have described and claimed in a separate application and which I briefly term hexaoxyanthraquinone it chiefly differs by its dyeing properties. The production of this new coloring-matter called alizarin hexacyanin may be carried out in the following different ways; first, by oxidizing alizarin pentacyanin or alizarin bordeaux in sulfuric acid solution with manganese dioxid, arsenic acid or other suitable oxidizing agents; secondly, by heating alizarin pentacyan'in with concentrated sulfuric acid at higher temperapurin (tetraoxyanthraquinone) which corre-' sponds with anthrapurpurin in a like manner as purpurin does with alizarin, is totally changed into alizarin hexacyanin by the further action of the oxidizing agents employed.
In carrying out the preceding three processes practically I proceed as follows: Ten
parts,-by weight, of dry alizarin pentacyanin' are dissolved in two hundred parts, by weight, of concentrated sulfuric acid of'66 Baum and five parts, by weight, of finely pulverized manganese dioxid containing ninety per cent. of dioxid, are gradually added. In the first place the quinone of alizarin pentacyanin, a so called anthradiquinone, is formed which may be recognized when a portion of the resulting mixture, dissolved in concentrated sulfuric acid, shows no more distinct absorption bands when looked at in the spec'- troscope. The quinone of alizarin pentacyanin, then, is converted into the quinone of alizarin hexacyanin by the further action of the manganese dioxid, employing advantageously a somewhat higher temperature. Therefore it is most practical to heat the mixture under continual stirring at a temperature of about centigrade until a test portion after pouring into water and boiling with acid sodium sulfite forms a precipitate the solution of which in concentrated sulfuric acid shows no more the absorption bands of alizarin pentacyanin. The resulting mixture then is poured intotwo thousand parts, by weight, of water: adding ten parts, by weight, of an aqueous acid sodium sulfite solution of 34 Baum. After heating to the boiling point the coloring-matter separating is filtered off and washed out. The latter is redissolved in the necessary quantity of soda-lye and the alkaline solution after having been filtered is decomposed by the addition of acids. The product precipitated is a mixture of alizarin hexacyanin and hexaoxyanthraquinone, as above mentioned. In order to remove the latter, the mixture is crystallized at first out of nitrobenzene, then repeatedly out of alco- 1101, in which the hexaoxyanthraquinone is more difficultly soluble than alizarin hexacyanin. A second and best method of separating the two coloring-matters of the above mixture is to be carried out by heating the mixture with sodium acetate and acetic acid anhydrid and boiling the resulting mixture of the two isomeric hexa-acetyl-compounds with acetone by which the hexa-acetyl derivative of hexaoxyanthraquinone is not dissolved while that of alizarin hexacyanin easily dissolves in the said solvent. By saponi fying the acetyl compounds thus separated the alizarin hexacyanin and hexaoxyanthraquinone are obtained in a pure state.
As alizarin pentacyanin is produced by oxidizing alizarin bordeaux, it is not necessary to start from alizarin pentacyanin but alizarin bordeaux may be employed without isolating the alizarin pentacyanin produced as an intermediate product.
The following is an example for the con version of alizarin bordeaux into alizarin hex acyanin: Ten parts, by weight, of dry alizarin bordeaux are dissolved in two hundred parts, by weight, of concentrated sulfuric acid at 66 Baum and fifteen parts, by weight, of finely pulverized manganese dioxid (containing ninety per cent. of dioxid) are gradually introduced, the temperature being kept at from 50 to 55 centigrade. The gradual conversion of alizarin bordeaux into alizarin pentacyanin and alizarin hexacyanin isto be recognized very distinctly by the usual spectroscopic examination. When the spectrum of the pentacyanin has totally disappeared the sulfuric acid liquid is treated in the same manner as described in the preceding example.
111 order to oxidize alizarin bordeaux in sulfuric acid solution by means of arsenic acid a higher temperature for example from to centigrade is necessary. The alizarin pentacyanin formed at first in this operation seems to be immediately converted into alizarin hexacyanin and hexaoxyanthraquinone, as in the spectroscopic examination of the oxidation products the alizarin pentacyanin is always to be recognized only in very small traces.
The following may be given as an example for the preparation of alizarin hexacyanin by oxidizing alizarin bordeaux by means of arsenic acid: A mixture of ten parts, by weight, of alizarin bordeaux, two hundred parts, by weight, of sulfuric acid at 66 Baum and fifteen parts, by weight, of dry arsenic acid are heated for about six hours at a temperature from 140 to 150 centigrade and the resulting mixture then is poured into water. By filtering off, redissolving in alkali and precipitating again with acids, separating the two products formed in the manner before described the alizarin hexacyanin dye-stuif is isolated.
Of course, on starting from alizarin pentacyanin in the last example a smaller quantity of arsenic acid is necessary for effecting the oxidation of alizarin pentacyanin into alizarin hexacyanin. At the high temperature employed in this example as well as in the following quinones are not formed as I have found the mixture contains the coloring matters and not the quinones thereof.
In order to produce alizarin hexacyanin by treating alizarin pentacyanin with concentrated sulfuric acid at higher temperatures I proceed as follows: Ten parts, by weight, of alizarin pentacyanin and two hundred parts, by weight, of sulfuric acid at 66 Baum are heated at centigrade until a sample of the mixture diluted with sulfuric acid shows no more the spectrum of alizarin pentacyanin. When the latter has been found to be totally converted the whole liquid is poured into water and the coloring matter separated by fil tering off, washing out and isolated in the manner above described.
Anthrapurpurin is converted into pure alizarin hexacyanin by an energetic oxidation with the aid of manganese dioxid. In the first place there is formed oxyanthrapurpurin which is a coloring-matter dyeing a yellowishred on cotton mordanted with alumina salts, but possesses only an inferior value for dyeing purposes. By the further oxidation the oxyanthrapurpurin is transformed into the quinone of alizarin hexacyanin and this quinone, is then converted into the cyanin (alizarin hexacyanin) by a subsequent treatment with reducing agents employing most practically sulfurous acid. The following example may illustrate how this operation is to be carried out: A pulverized mixture containing ten parts, by weight, of anthrapurpurin and nineteen parts, by weight, of manganese dioxid (ninety per cent.) is introduced with constant agitation into three hundred parts, by weight, of sulfuric acid at 66 Baum taking care that the temperature does not rise above 35 centigrade. After the whole manganese dioxid has been added, the mixture is allowed to stand for half an hour. Then it is poured into three thousand parts, by weight, of water mixed with ten parts, by weight, of an aqueous solution of sodium bisul fit at 55 Baum. The liquid is heated to the boiling point and the coloringinatter separated is filtered off, washed out and purified by redissolving, dad, in the well known manner.
I have further found that in general in order to Separate pure alizarin hexacyanin from other oxyanthraquinones especially in case the former be in excess the best method is the following: The mixture is dissolved in twenty times its weight of concentrated sulfuric acid and after heating to 100 centigrade water is gradually added to the cooled solution. In this manner the hexacyanine is precipitated at first and in a pure state as the other oxyanthraquinones, remain dissolved in the diluted sulfuric acid solution. The alizarin hexacyanin can readily be isolated by filtration.
My new product thus obtained and called alizarin hexacyanin is insoluble in water and very moderately soluble in alcohol with dark rose-red color and in glacial acetic acid with a more yellowish-red color both solutions showing a yellowish-bro wn fluorescence. Out of alcohol or glacial acetic acid it separates in dark brilliant crystals. It is easily soluble in boiling nitrobenzene and very easily in pyridin. Whenits alkaline solutions are decomposed by adding acids or on pouring its solution in concentrated sulfuric acid into water it separates in reddish-brown flakes which after filtering off yield a dark brown paste that is most fit for dyeing and printing purposes. It dissolves in sodium carbonate with bluish-violet color, in ammonia at first with dull brownish-violet color which gradually changesinto a pure and beautiful blue when the solution is allowed to stand in open vessels. By soda-lye it is dissolved with greenish-blue color and out of this solution when in contact with the atmospheric air dark violet flakes separate which I have found are the sodium salt of the quinone of alizarin hexaoyanin. Its solution in concentrated sulfuric acid possesses a bluish color and shows when looked at with the spectroscope two characteristic absorption bands namely: the one in the red part and the other between the yellow and green part of the spectrum. This sulfuric solution, however, assumes a color more greenish when it is allowed to stand for a longer time and thenthe hexaoxyanthraquinone described by mein a separate specification by the following properties: Alizarin hexacyanin dissolves in a solution of sodium carbonate with bluishviolet,.in soda-lye with greenish-blue color, dark violet flakes being separated out of such solution in soda-lye after some time in the air, in ammonia with dull brownish-violet color,
which changes into blue in the air, and in pure concentrated sulfuric acid with .blue color which turns green by standing and. on, adding water to such sulfuric acid solutionat first into violet, then into red, brownish-red. flakes being separated after some time. Hexaoxyanthraquinone. dissolves in a solution of. sodium carbonate with bluish-red, in sodalye with violet color which gradually turns into blue in the air blue flakes being further separated after some time, in ammonia liquid with bluish-red color which changes into violet in the air, in pure concentrated sulfuric acid with bluish-violet color which turns into yellowish-red on adding water, yellowish-brown flakes being separated after some time. The said alizarin derivatives further differ by the absorption spectra of their sulfuric acid solutions. Alizarin hexacyanin displays two strong absorption bands, the one in the red part and the other in the green part of the spectrum, while hexaoxyanthraquinone shows one strong absorption bandin the orange part and a slighter one in the yellowish-green part of the spectrum.
The shades produced by alizarin hexacyanin on wool mordanted with chromium or alumina salts are in general more greenish than those obtained by employing hexaoxyanthraquinone. It produces on wool mor-' danted with alumina salts violet, on W001 mordanted with chromium salts blue shades both being more greenish than those resulting from the alizarin pentacyanin and hexaoxyanthraquinone which I have described in separate specifications.
By analyzing the crystalized productl have found it to be a hexaoxyanthraquinone of the formula (J ,H,O (OH) isomeric with the hexaoxyanthraquinone obtained by me and described in a separate specification, Serial No; 412,304, filed November 18, 1891;
Having thus described my invention, what I claim as new, and desire to secure by Letters Patent, is-
1. The process of producing a new alizarin dye stuff by oxidizing alizarin pentacyanin or alizarin bordeaux, substantially as described.
2. The new dye herein described,insoluble in water, moderately soluble in alcohol and glacial acetic acid with yellowish-brown fluorescence, crystallizing from these solvents in dark brilliant crystals; easily soluble in boiling nitro benzol, and in pyridin; soluble in aqueous ammonia with a dull brownish color, which changes on exposure to air to a pure blue; soluble in alkali carbonates and caustic alkalies, from which solutions acids precipi-v tate the dye stud in. reddish-brown flakes, which,after filtering and washing, are a very suitable paste for use in the arts, producing IIO red and one between the yellow and green In testimony whereof I have signed my part of the spectrum, and assumes a more name in the presence of two subscribing witgreenish color 011 standing for a long time, at nesses.
the same time enlarging the absorption band ROBERT E. SCHMIDT. 5 in the red and diminishing the one between Witnesses:
the yellow and green part of the spectrum, XVM. ESSENWEIN,
having the qualities substantially as set forth. RUDOLPH FRIEKE.
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