US677239A - Halogen-substituted indigo and process of making same. - Google Patents
Halogen-substituted indigo and process of making same. Download PDFInfo
- Publication number
- US677239A US677239A US426500A US1900004265A US677239A US 677239 A US677239 A US 677239A US 426500 A US426500 A US 426500A US 1900004265 A US1900004265 A US 1900004265A US 677239 A US677239 A US 677239A
- Authority
- US
- United States
- Prior art keywords
- indigo
- halogen
- making same
- chlor
- para
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229940097275 indigo Drugs 0.000 title description 14
- 235000000177 Indigofera tinctoria Nutrition 0.000 title description 12
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 title description 12
- 238000000034 method Methods 0.000 title description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000006467 substitution reaction 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
- 210000002268 wool Anatomy 0.000 description 2
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 1
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical class [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- -1 bisulfite compound Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000001550 testis Anatomy 0.000 description 1
- 238000005406 washing Methods 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
- C09B7/00—Indigoid dyes
- C09B7/02—Bis-indole indigos
- C09B7/04—Halogenation thereof
Definitions
- Halogen substitution products of indigo are already known 5 but all these known products most closely resemble indigo, not merely in their property of subliming and the like, but also in yielding a vat from which they can be dyed and in dyeing the various fibers giving blue shades.
- Our present invention relates to the manufacture of a new halogen-substituted indigo coloring-matter which resembles indigo in the chemical properties, in its manner of being dyed, and in the fastness of the shades obtained, but which differs from indigo and from the hitherto-known halogen substitution compounds thereof in that the color obtained by dyeing with it is a brilliant redviolet. If this new coloring-matter be treated with fuming sulfuric acid or other sulfonating agent, a soluble sulfo-acid is obtained which, however, dyes wool from the acid-bath blue shades.
- the new coloring-matter can be conveniently obtained, starting from para-chlor-ortho-nitro-toluene. (See Berz'chte,Vol. 19, page 2240.)
- This body is oxidized by means of manganese peroxid in sulfuric acid, prefer-- ably at a high temperature, so as to obtain para-chlor-ortho nitro benzaldehyde.
- This ortho-nitro benZaldehyde derivative is then converted by treatment with acetone and alkali into the new indigo coloring-matter.
- Example 1- Owidation ofpara-chlonorthom'tro ioluoL-Mix together one hundred parts of para-chlor-ortho-nitro-toluene, about one hundred (100) parts of manganese peroxid, (containing about eighty per cent. MnO and two thousand (2,000) parts of sulfuric acid, (containing about sixty-three per cent. H 80 Heat this mixture for about four to five hours and at a temperature of from to centigrade in a lead-lined vessel furnished with an inverted condenser. Then the oxidation is finished, allow the liquid to stand until practically clear. Then separate the acid from the oil and wash the oil successively with water and with a solution of carbonate of soda. Next treat the said oil with sodium bisulfite, so as to obtain the crystalline bisulfite compounds of the alde hyde. Dissolve this in water and decompose it with alkali or acid. Collect in any suit able way.
- the new coloring-matter so obtained is a brown-red powder, which on rubbing with a hard body gives an intensely-black metallic streak. Upon heating it sublimes, evolving violet-red vapors, which yield a crystalline sublimate. It is insoluble in the ordinary solvents, but is soluble in boiling nitro-benzene or anilin, (the solutionsbeiug vi0let-red,) from which on cooling it separates out.
- the new indigo derivative can be dyed like the ordinary indigo from the vat, and it dyes wool and cotton in this way violet-red shades which are fast to washing and to light. On treatment with fuming sulfuric acid or othersu'lfonating agent it yields a sulfo-acid, and
- coloring-matter which consists in treating para-chlor-orthonitro-benzaldehyde with acetone and an alkali, substantially as described.
- testi mony whereof we have hereunto set our hands in the presence of two subscribing witnesses.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
ihvrrn STATES RUDOLF KNIETSOH AND ROBERT I-IOLDMANN, OF LUDVIGSHAFEN, GER- MANY, ASSIGNORS TO THE BADISOHE ANILIN d: SODA FABRIK, OF SAME PLACE.
HALOGEN-SUBSTITUTED INDIGO AND PROCESS OF MAKING SAME.
SPECIFICATION forming part of Letters Patent No. 677,239, dated June 25, 1901.
Application filed February 6, 1900. Serial No. 4,265, (No specimens.)
To all who/72 in may concern:
Be it known that we, RUDOLF KNIETSCH, doctor of philosophy, asubject of the King of Prussia, German Emperor, and ROBERT HOLD- MANN, a subject of the King of Bavaria, both residing at Ludwigshafen-on-the-Rhine, in the Kingdom of Bavaria and Empire of Germany,haveinvented newand useful Improvements in New Indigo Coloring- Matters, of which the following is a specification.
Halogen substitution products of indigo are already known 5 but all these known products most closely resemble indigo, not merely in their property of subliming and the like, but also in yielding a vat from which they can be dyed and in dyeing the various fibers giving blue shades.
Our present invention relates to the manufacture of a new halogen-substituted indigo coloring-matter which resembles indigo in the chemical properties, in its manner of being dyed, and in the fastness of the shades obtained, but which differs from indigo and from the hitherto-known halogen substitution compounds thereof in that the color obtained by dyeing with it is a brilliant redviolet. If this new coloring-matter be treated with fuming sulfuric acid or other sulfonating agent, a soluble sulfo-acid is obtained which, however, dyes wool from the acid-bath blue shades.
The new coloring-matter can be conveniently obtained, starting from para-chlor-ortho-nitro-toluene. (See Berz'chte,Vol. 19, page 2240.) This body is oxidized by means of manganese peroxid in sulfuric acid, prefer-- ably at a high temperature, so as to obtain para-chlor-ortho nitro benzaldehyde. This ortho-nitro benZaldehyde derivative is then converted by treatment with acetone and alkali into the new indigo coloring-matter. This can be either done directly or the intermediate para-chlor-ortho-nitro-phenol-lacticacid-methyl-ketone can be isolated and either be used as such or after conversion into its bisulfite compound for conversion into indigo by treatment with alkali. This conversion can either be effected on the fiber or not.
The following examples will serve to further illustrate our invention and the manner in which it can best be carried into practical effect, the parts being by weight:
Example 1- Owidation ofpara-chlonorthom'tro ioluoL-Mix together one hundred parts of para-chlor-ortho-nitro-toluene, about one hundred (100) parts of manganese peroxid, (containing about eighty per cent. MnO and two thousand (2,000) parts of sulfuric acid, (containing about sixty-three per cent. H 80 Heat this mixture for about four to five hours and at a temperature of from to centigrade in a lead-lined vessel furnished with an inverted condenser. Then the oxidation is finished, allow the liquid to stand until practically clear. Then separate the acid from the oil and wash the oil successively with water and with a solution of carbonate of soda. Next treat the said oil with sodium bisulfite, so as to obtain the crystalline bisulfite compounds of the alde hyde. Dissolve this in water and decompose it with alkali or acid. Collect in any suit able way.
Example 2-O0noersion 0f pura-chlor-ortho-ml2fr0benealdchydc into para-di-chlor-indigo.Prepare a mixture of one hundred (100) parts of para-chlor-ortho-nitro-benzaldehyde, four hundred (400) parts of acetone, and one hundred (100) parts of water. To this mixture add gradually while keeping the whole mass cool one thousand (1,000) parts of dilute caustic-soda lye, (containing one per cent. of NaOl-I.) The para-di-chlor-indigo soon begins to separate out. Collect by filtering, wash, and dry.
The new coloring-matter so obtained is a brown-red powder, which on rubbing with a hard body gives an intensely-black metallic streak. Upon heating it sublimes, evolving violet-red vapors, which yield a crystalline sublimate. It is insoluble in the ordinary solvents, but is soluble in boiling nitro-benzene or anilin, (the solutionsbeiug vi0let-red,) from which on cooling it separates out. The new indigo derivative can be dyed like the ordinary indigo from the vat, and it dyes wool and cotton in this way violet-red shades which are fast to washing and to light. On treatment with fuming sulfuric acid or othersu'lfonating agent it yields a sulfo-acid, and
2. The process of making coloring-matter which consists in treating para-chlor-orthonitro-benzaldehyde with acetone and an alkali, substantially as described.
In testi mony whereof we have hereunto set our hands in the presence of two subscribing witnesses.
RUDOLF KNIETSCII. ROBERT HOLDMANN.
Witnesses:
ERNEST F. EHRHARDT, JACOB ADRIAN.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US426500A US677239A (en) | 1900-02-06 | 1900-02-06 | Halogen-substituted indigo and process of making same. |
| US48784A US677240A (en) | 1900-02-06 | 1901-02-25 | Indigo sulfo-acid. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US426500A US677239A (en) | 1900-02-06 | 1900-02-06 | Halogen-substituted indigo and process of making same. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US677239A true US677239A (en) | 1901-06-25 |
Family
ID=2745786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US426500A Expired - Lifetime US677239A (en) | 1900-02-06 | 1900-02-06 | Halogen-substituted indigo and process of making same. |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US677239A (en) |
-
1900
- 1900-02-06 US US426500A patent/US677239A/en not_active Expired - Lifetime
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