US805890A - Diamidoformyl diphenylamin and process of making same. - Google Patents
Diamidoformyl diphenylamin and process of making same. Download PDFInfo
- Publication number
- US805890A US805890A US14183203A US1903141832A US805890A US 805890 A US805890 A US 805890A US 14183203 A US14183203 A US 14183203A US 1903141832 A US1903141832 A US 1903141832A US 805890 A US805890 A US 805890A
- Authority
- US
- United States
- Prior art keywords
- para
- diamidoformyl
- diphenylamin
- making same
- iron
- 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
- 238000000034 method Methods 0.000 title description 8
- 230000008569 process Effects 0.000 title description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229940032330 sulfuric acid Drugs 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 241001112285 Berta Species 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- -1 dinitro compound Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 241001385464 Acidon Species 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102000006835 Lamins Human genes 0.000 description 1
- 108010047294 Lamins Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 210000005053 lamin Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DKLYDESVXZKCFI-UHFFFAOYSA-N n,n-diphenylacetamide Chemical compound C=1C=CC=CC=1N(C(=O)C)C1=CC=CC=C1 DKLYDESVXZKCFI-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
Definitions
- Para-para1-diamidodiphenylamin has hitherto been obtained by reducing indamin; but as this process is inconvenient and the yield is not good a simpler and cheaper method for obtaining this technically-valuable base'has been sought.
- the dinitroacidyl compounds used as parent material namely, para-paral-dinitroformyldiphenylamin and para-parai-dinitroacetyldiphenylamin-may be obtained by di-nitrating the formyldiphenylarnin produced by the action of formic acidon diphenylmin (Berta/life, VIII, 1,195) or the acetyldiphenylamin in a sulfuric-acid solution containing a mixture of nitric and sulfuric acid (Ber. XIV, 2,366) in a similar manner as described in the Zeitschmlfif f. (mgew. Uhemz'e, 1899, p.1,051. The nitrated mixture is then poured into ice-water and the precipitate of feeble-yellow color is filtered, washed, and dried.
- the reduction and hydrolysis may be carried out, for instance, as follows: Fourteen kilograms of finely-ground dinitroformyldiphenylamin, mixed With water, are slowly introduced into a mixture of thirty kilograms of iron-filings, two hundred and fifty liters of water,and about one -half kilogram of sulfuric acid of 66 Baum, specific gravity, heated to 60 to 90 centigrade. The whole is stirred at this temperature (about five hours) until the precipitate suspended in the reduced mass no longer appears brown. but black. The mass when cooled to 40 to 50 centigrade is then directly treated with 20-40 kilograms of sulfuric acid of fifty per cent. strength until an acid reaction sets in and hydrogen begins tov be evolved.
- the filtrate which is obtained by acidifying the reduced mass with sulfuric acid, may be treated with about ten kilograms of sulfuric acid of 66 Baum, specific gravity, and then boiled.
- the difficultly-soluble sulfate of para-paral-diamidodiphenylamin then separates, forming a magma, while small proportions of isomeric bases remain in suspension.
- the para-parm-diamidoformyl- (acetyl) -diphenylamin is to serve for the manufacture of dyestuffs and diamidodiphenylamin.
- diamidodiphenylamin which consists in reducing dinitroformyldiphenylamin with iron and then decomposing the diamidoformyldiphenylamin by heating it with acids.
- para-para1 diamidoformyldiphenylamin having the formula HCO- OTTO SOHST.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
UNITED STAT S- BATENT OFFICE.
OTTO soHsT, OF'HOOHST-ONQTHEMAIN, GERMANY, ASSIGNOR TO FARBWERKE, VORM. MEISTER, uc us & RUNING, OF ooHsT- ON-THE-MAIN, GERMANY, A oonr fonAT on on GERMANY.
DIAMIDOFORMYL DIPfiENYLAMlN AND PROCESS F MAKING SAME.-
Specification of Letters Patent.
Patented Nov. 28, 1905.
ApplicatiOll filed February 4. 1903. Serial No. 141,832. (Specimens)- citizen of the Empire of Germany, residing at -H6chst-on-the-Main, Germany, have invented certain new and useful Improvements in Para-Para1-Diamidoacidyldiphenylamin and its Transformation into Diamidophenylamin, of which the following is a specification.
Para-para1-diamidodiphenylamin has hitherto been obtained by reducing indamin; but as this process is inconvenient and the yield is not good a simpler and cheaper method for obtaining this technically-valuable base'has been sought.
The para-para1-dinitrodiphenylamin (Zeitsc/zm'ft f. ange'w. Ohemt'e, 1899, 1,051, and Berta/Lie, XVI, 2,576) readily obtainable by the nitration of acidy-l derivatives of diphenylalnin and subsequent hydrolysis'appears not to be suitable as parent material, for hitherto its reduction was only possible by use of the expensive stannous chlorid or zinc-dust and glacial acetic acid. (See above references.)
Nothing has been known hitherto about reducing the para-paraldinitrodiphenylamin with the comparatively cheap reducing agent, iron. Experiments have shown that it is possible to reduce the dinitro compound with iron; but the product cannot be separated in a pure state from the iron and in a rational manner, giving a good. yield.
By operating, for instance, in the manner already described in Bem'ohte, XXVIII, 2, 969, for ortho-para-dinitrodiphenylamin the yield of pure base is very moderate, and as the parap'arardiamidodiphenylamin is less soluble than the ortho-para-compound a large pro: portion of water is requisite to isolate the base from the reduced mass, and for this reason alone this mode of working is technically in applicable.
I have found that by using iron the reduction occurs more smoothly if for ,dinitrodi-.
phenylamin the acidyl-dinitrodiphenylamin is used; but by this modification the process does not become available for industrial purposes, for it is just as difficuit to isolate the.
ric or, better still, sulfuric acid without any decomposition or formation of color, as is the case, for instance, when operating with parapara1- or ortho-paradinitrodiphenylamim 'The acidyl-paraparal-diamidodiphenylamin, hitherto unknown, is readily obtained with a good yield by this process.
It is easily hydrolyzed. When heated with a an excess of sulfuric acid, it is transformed into para para1 diamidodipheny lamin. For
sulfate of para-paral-diamidodiphenylamin crystallizes when the solution is cold.
The dinitroacidyl compounds used as parent material namely, para-paral-dinitroformyldiphenylamin and para-parai-dinitroacetyldiphenylamin-may be obtained by di-nitrating the formyldiphenylarnin produced by the action of formic acidon diphenylmin (Berta/life, VIII, 1,195) or the acetyldiphenylamin in a sulfuric-acid solution containing a mixture of nitric and sulfuric acid (Ber. XIV, 2,366) in a similar manner as described in the Zeitschmlfif f. (mgew. Uhemz'e, 1899, p.1,051. The nitrated mixture is then poured into ice-water and the precipitate of feeble-yellow color is filtered, washed, and dried.
According to the above observations the reduction and hydrolysis may be carried out, for instance, as follows: Fourteen kilograms of finely-ground dinitroformyldiphenylamin, mixed With water, are slowly introduced into a mixture of thirty kilograms of iron-filings, two hundred and fifty liters of water,and about one -half kilogram of sulfuric acid of 66 Baum, specific gravity, heated to 60 to 90 centigrade. The whole is stirred at this temperature (about five hours) until the precipitate suspended in the reduced mass no longer appears brown. but black. The mass when cooled to 40 to 50 centigrade is then directly treated with 20-40 kilograms of sulfuric acid of fifty per cent. strength until an acid reaction sets in and hydrogen begins tov be evolved. It is then filtered, and when cold the base is separated from the filtrate by adding sodium acetate. The diamidoformyldiphenylamin is thus obtained as small slightlycolored crystals having the formula To obtain the para-paral-diamidodiphenylamin, the filtrate, which is obtained by acidifying the reduced mass with sulfuric acid, may be treated with about ten kilograms of sulfuric acid of 66 Baum, specific gravity, and then boiled. When cold, the difficultly-soluble sulfate of para-paral-diamidodiphenylamin then separates, forming a magma, while small proportions of isomeric bases remain in suspension.
If fordinitroformyldiphenylamin dinitroacetyldiphenylamin is used, the same products may be obtained. The hydrolysis, however, is somewhat slower.
The para-parm-diamidoformyl- (acetyl) -diphenylamin is to serve for the manufacture of dyestuffs and diamidodiphenylamin.
Having now described my invention, whatI claim is- 1. The process of making diamidoformyldiphenylamin, which consists in reducing dinitroformyldiphenylamin with iron in the presence of little acid, separating the base from the excess of iron by means of the easily-soluble sulfate and then isolating it with sodium acetate.
2. The process of making diamidodiphenylamin, which consists in reducing dinitroformyldiphenylamin with iron and then decomposing the diamidoformyldiphenylamin by heating it with acids.
3. As a new article of manufacture, the
para-para1 diamidoformyldiphenylamin having the formula HCO- OTTO SOHST.
Witnesses ALFRED BRISBOIS, BERNHARD LEYDECKER.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14183203A US805890A (en) | 1903-02-04 | 1903-02-04 | Diamidoformyl diphenylamin and process of making same. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14183203A US805890A (en) | 1903-02-04 | 1903-02-04 | Diamidoformyl diphenylamin and process of making same. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US805890A true US805890A (en) | 1905-11-28 |
Family
ID=2874373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US14183203A Expired - Lifetime US805890A (en) | 1903-02-04 | 1903-02-04 | Diamidoformyl diphenylamin and process of making same. |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US805890A (en) |
-
1903
- 1903-02-04 US US14183203A patent/US805890A/en not_active Expired - Lifetime
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