USRE23389E - Nitro-ihiophantbraquinones - Google Patents
Nitro-ihiophantbraquinones Download PDFInfo
- Publication number
- USRE23389E USRE23389E US23389DE USRE23389E US RE23389 E USRE23389 E US RE23389E US 23389D E US23389D E US 23389DE US RE23389 E USRE23389 E US RE23389E
- Authority
- US
- United States
- Prior art keywords
- nitro
- parts
- thiophanthraquinone
- melting
- acid
- Prior art date
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- 238000002844 melting Methods 0.000 description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N Nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 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 4
- 239000002253 acid Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- -1 nitro-(2- thenoyl) Chemical group 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000717 retained Effects 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 description 1
- ROFZMKDROVBLNY-UHFFFAOYSA-N 4-nitro-2-benzofuran-1,3-dione Chemical compound [O-][N+](=O)C1=CC=CC2=C1C(=O)OC2=O ROFZMKDROVBLNY-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/74—Naphthothiophenes
Definitions
- This invention relates to new thiophanthraquinones, and more particularly to the preparation of nitro-substituted thiophanthraquinones of the formula:
- thiophanthraquinone is employed in the naming of this compound in view of the original name used by Scholl and Seer in Ann. 394, 131 (1912), who designated the corresponding unsubstituted hydrocarbon compound thicphanthracene.
- a further object of the invention is to provide a commercially feasible process for the preparation of these new nitrothiophanthraquinones.
- nitrothiophanthraquinones of this invention may be made by ring closing the nitro-(2- thenoyl) -o-benzoic acids disclosed in co -pending application Serial No. 723,676, now U. S. Patent 2,513,573, which, in turn, may be prepared by reacting the nitro-substituted phthalic anhydrides with the Grignard reagent prepared from 2-bromothiophene or 2-iodothiophene, or by condensation of the corresponding nitro-phthalic anhydride with thiophene by the aid of aluminum chloride or similar condensing agent.
- nitro-thiophanthraquinones may be reduced to the aminothiophanthraquinones for use in the manufacture of dyestuffs, as more particularly disclosed in co-pending application Serial No. 723,672, now U. S. Patent 2,501,132.
- Example 3 Twenty-eight (28) parts of anhydrous aluminum chloride were dissolved in 150 parts of nitrobenzene. Ten (10) parts of [5-nitr0-(2- thenoyD-o-benzoic acid] 4-nitro-(2-thenoyl) -obenzoic acid, melting range 149 150 C., were added, and the reaction mass was heated to from to C. for 24 hours. It was then poured into dilute hydrochloric acid and the nitrobenzene was removed with steam. The residue was filtered, washed, dried, and extracted with toluene in a Soxhlet apparatus. The extract was evaporated to dryness, and the 9.3 parts obtained were dissolved in 850 parts of chlorobenzene at about 25 C.
- Example 4 Twenty-eight ,(28) parts of anhydrous aluminum chloride were dissolved in 150 parts of nitrobenzene. Ten parts of [4-nitro-(2- thenoyll-o-benzoic acid] 5-mtro- (.Z-thenoyl) -0- benzoic acid, melting range 189190 0., were added, the temperaturewas raised to 125 C. in
- Example 5 3.5 parts of [4-nitro-(2-thenoyl)-o-benzoic acid] 5-nitro-(2-then0yl) -o-benzoic acid, melting range 189-190 C., and 1.5 parts of boric acid were dissolved in 36 parts of sulfuric acid. The solution was heated at from to C. for about 30 minutes and then poured on ice. The precipitate was filtered, washed, slurried in Warm dilute caustic, filtered, Washed again and dried. 1.5 parts of crude nitro-thiophanthraquinone, melting at from 228 to 232 C., was obtained. It was identical with the mixture of 6- and '7-nitro-thiophanthraquinones obtained by the method described in the preceding example.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
Reissued July 10, 1951 23,389 NIIRO -THIOPHA15THRAQUINONES Henry R. Lee and Viktor V/eininayr, Pitinan, N. J
assignors to E. I. du Font de Nemours & Company, Wilmington, Del, a corporation of Bela- No Drawing. Original No. 2,501,131, dated March 21, 1950, Serial No. 723,671, January 22, 1947. Application for reissue February 9, 1951, Serial 3 Claims.
Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
This invention relates to new thiophanthraquinones, and more particularly to the preparation of nitro-substituted thiophanthraquinones of the formula:
wherein any one of the positions [5, 6, l and 8 carry] 5 and 7 carries a nit-r group, While the remaining positions are unsubstituted.
The term thiophanthraquinone is employed in the naming of this compound in view of the original name used by Scholl and Seer in Ann. 394, 131 (1912), who designated the corresponding unsubstituted hydrocarbon compound thicphanthracene.
It is an object of this invention to prepare new nitro-thiophanthraquinones which are useful as starting materials for the preparation of other compounds, and particularly as intermediates for the synthesis of dyes. A further object of the invention is to provide a commercially feasible process for the preparation of these new nitrothiophanthraquinones.
The nitrothiophanthraquinones of this invention may be made by ring closing the nitro-(2- thenoyl) -o-benzoic acids disclosed in co -pending application Serial No. 723,676, now U. S. Patent 2,513,573, which, in turn, may be prepared by reacting the nitro-substituted phthalic anhydrides with the Grignard reagent prepared from 2-bromothiophene or 2-iodothiophene, or by condensation of the corresponding nitro-phthalic anhydride with thiophene by the aid of aluminum chloride or similar condensing agent. These nitro-thiophanthraquinones may be reduced to the aminothiophanthraquinones for use in the manufacture of dyestuffs, as more particularly disclosed in co-pending application Serial No. 723,672, now U. S. Patent 2,501,132.
The following examples are given to illustrate the invention. The parts used are by weight.
Example 1 Two (2) parts of [6-nitro-(2-thenoyD-obenzoic acid] 3-mtro- (2 thenoyl) -o-benzoic acid,
of 216-21'7 0., of the COOH I i] with a melting range formula:
were dissolved in 36 parts of sulfuric acid and the solution was heated at 145 to 150 C. for 2 minutes. The deep red solution was then cooled to below C., and water was added below that temperature to dilute the mass to an acidity of about 25%. The E8-nitro-thiophanthraquinone] 5mitro-thiophanthraquinome, precipitated in a crystalline form, was filtered off, washed acid free, and slurrled in a dilute solution of sodium carbonateto remove unring-closed [6-nitro- (Z-thenoyl) -0-benzoic acid] 3-m'tro- (Z-themoyl) o-beneoic acid. After again filtering, washing free of alkali and drying, 0.6 part of [B-nitrothiophanthraquinone] 5-nitm-thiophanthraquinone was obtained melting at 230-23l C. It was crystallized several times from 20 parts of chlorobenzene per part of crude product and had a final melting range from 234-235 0.
Example .2
Two (2) parts of [3-m'tro-(2-thenoyl) -0-benzoic acid] G-nztro-(Z-thenoyl) -o-benzoic acid, melting range 169-170 C., were dissolved in 36 parts of 95% sulfuric acid and the solution was heated to 148 to 152 C. for several minutes. The reaction mass was worked up as described for the nitro-thi0phanthraquin0ne in Example 1. 0.65 part of [8-nitro-thiophanthraquinone] S-m'trothiophanthraquinone was obtained, melting at from 230-23l C. It was crystallized several times from 37 parts of chlorobenzene per part of crude product, and melted finally at from 235"- 236 C.
Example 3 Twenty-eight (28) parts of anhydrous aluminum chloride were dissolved in 150 parts of nitrobenzene. Ten (10) parts of [5-nitr0-(2- thenoyD-o-benzoic acid] 4-nitro-(2-thenoyl) -obenzoic acid, melting range 149 150 C., were added, and the reaction mass was heated to from to C. for 24 hours. It was then poured into dilute hydrochloric acid and the nitrobenzene was removed with steam. The residue was filtered, washed, dried, and extracted with toluene in a Soxhlet apparatus. The extract was evaporated to dryness, and the 9.3 parts obtained were dissolved in 850 parts of chlorobenzene at about 25 C. The clear solution was passed through a column packed with alumina which had been activated by heating at 325 to 350 C'. Most of the impurities were retained on the alumina While the solution of the partially purifled [6 nitro thiophanthraquinone] 7 nitrothiophawthraquinone passed slowly through the column. Upon evaporation of this filtrate, 4.4 parts of crude [6-nitro-thiophanthraquinone] 7-nitrophanthraquinone were obtained, melting from 228 to 230 C. It was crystallized several times from 16 parts of chlorobenzene per part of crude product, and [S-nitro-thiophanthraquinone] 7 nitro thiophanthraquinone, melting from 233- 234 C'., was obtained.
A mixed meltingpoint of this nitro-thiophanthraquinone, with the [8-nitro-thiophanthraquinone] -nitro -thiophanthraquinone, showed a strong depression.
Example 4 Twenty-eight ,(28) parts of anhydrous aluminum chloride were dissolved in 150 parts of nitrobenzene. Ten parts of [4-nitro-(2- thenoyll-o-benzoic acid] 5-mtro- (.Z-thenoyl) -0- benzoic acid, melting range 189190 0., were added, the temperaturewas raised to 125 C. in
.4 hours, and kept at from 125 to 130 C. for 18 hours. The reaction mass was then poured into jhydrochloricacid and the m'trobenzene was removed with steam. The residue was filtered, Washed, dried and slurried in 1100 parts of chlorobenzene at about 25 C. The insoluble ma- :terial was removed by filtration and the clear solution was passed through a column containing alumina which had been activated by heatat from,325 to 350 C. Most of the impurities were retained on the alumina while the solution of the nitro-thiophanthraquinone passed slowly through the column. This filtrate was evaporated to dryness and 3.5 parts of crude nitro-thiophanthraquinone, melting from 225 to 230 C., were obtained. It was crystallized several times from about 18 parts of chlorobenzene per part of crude product, and was then isolated in pure form, melting at, 2 3 2233 C. The final product of this example is a mixture of 6- and "L-nitro-thiophanthraquinones.
4 Example 5 3.5 parts of [4-nitro-(2-thenoyl)-o-benzoic acid] 5-nitro-(2-then0yl) -o-benzoic acid, melting range 189-190 C., and 1.5 parts of boric acid were dissolved in 36 parts of sulfuric acid. The solution was heated at from to C. for about 30 minutes and then poured on ice. The precipitate was filtered, washed, slurried in Warm dilute caustic, filtered, Washed again and dried. 1.5 parts of crude nitro-thiophanthraquinone, melting at from 228 to 232 C., was obtained. It was identical with the mixture of 6- and '7-nitro-thiophanthraquinones obtained by the method described in the preceding example.
The processes as described in the above example may of course be varied in ways obvious to those skilled in the art. While sulfuric acid or' in which the N02 group is in one of the positions [5, 6, '7 and 8] 5 and 7 while the remaining positions are substituted with hydrogen.
2. 7-nitro-thiophanthraquinone.
[3. 6-nitro-thiophanthraquinone.]
4. [8 nitro thiophanthraquinone] .5 nitrothiophunthraquinone.
HENRY R. LE VIKTOR WECLNMAYR.
REFERENCES CITED The following references are of record in the file of this patent or the original patent:
Thomas: pages 510, 540. ReinholdP-ub. C0,, N. Y., 1911.
Steinkopf: Ann. 107, 99,107, 108 (1914).
Anhydrous Aluminum Chloride,
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Publication Number | Publication Date |
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USRE23389E true USRE23389E (en) | 1951-07-10 |
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US23389D Expired USRE23389E (en) | Nitro-ihiophantbraquinones |
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