US2208678A - Process for the production of dibenzylsulphanilic acid - Google Patents
Process for the production of dibenzylsulphanilic acid Download PDFInfo
- Publication number
- US2208678A US2208678A US192962A US19296238A US2208678A US 2208678 A US2208678 A US 2208678A US 192962 A US192962 A US 192962A US 19296238 A US19296238 A US 19296238A US 2208678 A US2208678 A US 2208678A
- Authority
- US
- United States
- Prior art keywords
- acid
- production
- dibenzylsulphanilic
- dibenzylsulphanilate
- mols
- 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
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- 238000000034 method Methods 0.000 title description 20
- DHRZHJZKNWAIJE-UHFFFAOYSA-N 4-(dibenzylamino)benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1N(CC=1C=CC=CC=1)CC1=CC=CC=C1 DHRZHJZKNWAIJE-UHFFFAOYSA-N 0.000 title description 16
- 238000004519 manufacturing process Methods 0.000 title description 15
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 19
- 229950000244 sulfanilic acid Drugs 0.000 description 17
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 15
- 229940073608 benzyl chloride Drugs 0.000 description 15
- 238000009835 boiling Methods 0.000 description 12
- 239000012736 aqueous medium Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003518 caustics Substances 0.000 description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- LJPQSZVZLDUAQO-UHFFFAOYSA-N 4-(benzylamino)benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1NCC1=CC=CC=C1 LJPQSZVZLDUAQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003513 tertiary aromatic amines Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000287181 Sturnus vulgaris Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/30—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/37—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
Definitions
- Example I The heretofore known processes for the production of dibenzylsulphanilic acid yield mixtures of sulphanilic acid, monobenzylsulphanilic acid and dibenzylsulphanilic acid. By using our process, theoretical yields and c. p. dibenzylsulphanilate is obtained. The purity is evidenced in the great improvement in shades obtained in conjunction with application of dyes.
- the reaction mass is then discharged into water and acidified to Congo with H01. Upon standing and stirring the mass crystallizes. The crystals are filtered and washed with dilute cold muriatic acid until free from calcium. The compound may then be either dried or converted to the metal salt by treating with the quantitative amount of metal hydroxide or carbonate. The yield is 353 parts of the free acid or 375 parts of the sodium salt.
- Example II 173 grams of sulphanilic acid are suspended in 1000 c. c. of water and 395 grams dimethyl aniline added. The mixture is heated to reflux and 280 grams of benzyl chloride added in portions, allowing each portion to react before further addition. Refluxed one hour after all has been added. The reaction mass is allowed to cool to 80 C. and a strong sodium carbonate solution is carefully added until a slight test is obtained on phenolphthalein paper.
- a process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols of benzyl chloride in the presence of an alkaline earth metal hydroxide.
- a processfor the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols of benzyl chloride at an alkalinity between pH 7.5 and pH 8.3 in the presence of an alkaline earth metal hydroxide.
- a process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols of benzyl chloride in the presence of a tertiary aromatic amine.
- a process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols of benzyl chloride at an alkalinity between pH 7.5 and pH 8.3 in the presence of a tertiary aromatic amine.
- a process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of slaked lime.
- a process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of sulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of dimethylaniline.
- a process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of dimethylaniline at an alkalinity between pH 7.5 and pH 8.3.
- a process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of pyridine.
- a process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of pyridine at an alkalinity between pH 7.5 and pH 8.3.
- a process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of mild acid binding agents selected from the group of alkaline earth metal hydroxides, pyridine, and tertiary aromatic amines.
Description
Patented July 23, 1940 UNITE-D stares PATENT orries PaooEss FOR THE. PRODUCTION OF DIBENZYLSULPHANILIG Aom Eugene A. Markush, Jersey Ci y, N. J., John J. Malawista, Brooklyn, N. Y., and Julius Miller, Newark, N. J., assignors to PharmaOhemical Corporation; New York, N. Y., a corporation of New York No Drawing. Application February 28, 1938,
Serial No. 192,962
11 Claims.
. to these known processes.
We have found that the above-mentioned objectionable features incident to the previously suggested processes result from the employment of strong alkalies during the production period and to the use of previously advised caustic alkali hydroxides, such as sodium hydroxide and potassium hydroxide.
We have further found that the above-described undesirable results are obtained by the use of caustic alkaline hydroxides even when the alkalinity of the reaction mass is maintained between pH 7.5 and pH 8.2, thus indicating that these objectionable results are produced by the employment of caustic alkaline hydroxides.
We have found that if the reaction between sulphanilic acid and benzyl chloride be conducted in the presence of mild acid-binding compounds instead of in the presence of caustic alkaline hydroxides, much greater yields of dibenzylsulphanilic acid with decreased quantities of monobenzylsulphanilic acid and unconverted sulphanilic acid are obtained than are producible by the former known processes.
We have further found that if the operation of our process be conducted in an alkalinity of between pH 7.5 and pH 8.3 almost theoretical yields of dibenzylsulphanilic acid are obtained with the production of practically no monobenzylsulphanilic acid and with practically no unconverted sulphanilic acid. -In fact we have thus obtained theoretical yields, and hence we prefer to maintain this degree of alkalinity in our process.
That the undesirable results of the previously known process are due to the employment of caustic alkaline hydroxides is shown by our extended experiments in which we have found that the successful results of our invention are not limited to the use of any particular chemical class of mild acid binding-compounds, but includes alkali earth hydroxides such as calcium hydroxide, magnesium hydroxide, strontium hydroxide, and tertiary amines such as pyridine, dimethyl aniline and triethanolamine, and hence by the Words mild acid-binding agents we mean those compounds which have mild acid-binding properties in contradistinction to those having strong caustic alkalinity such as sodium hy-' droxide and potassium hydroxide.
We give the following as examples of the process of our invention:
Example I The heretofore known processes for the production of dibenzylsulphanilic acid yield mixtures of sulphanilic acid, monobenzylsulphanilic acid and dibenzylsulphanilic acid. By using our process, theoretical yields and c. p. dibenzylsulphanilate is obtained. The purity is evidenced in the great improvement in shades obtained in conjunction with application of dyes.
173 parts sulphanilic acid suspended in 1000 parts water and 120 parts slaked lime added and the mixture is heated to reflux temperature.
278 parts benzyl chloride are added in portions so that the reaction proceeds smoothly. After all has been added, the boiling is continued for another 15 minutes and the excess benzylchloride distilled oif.
The reaction mass is then discharged into water and acidified to Congo with H01. Upon standing and stirring the mass crystallizes. The crystals are filtered and washed with dilute cold muriatic acid until free from calcium. The compound may then be either dried or converted to the metal salt by treating with the quantitative amount of metal hydroxide or carbonate. The yield is 353 parts of the free acid or 375 parts of the sodium salt.
Example II 173 grams of sulphanilic acid are suspended in 1000 c. c. of water and 395 grams dimethyl aniline added. The mixture is heated to reflux and 280 grams of benzyl chloride added in portions, allowing each portion to react before further addition. Refluxed one hour after all has been added. The reaction mass is allowed to cool to 80 C. and a strong sodium carbonate solution is carefully added until a slight test is obtained on phenolphthalein paper.
The dimethyl aniline is then blown off with steam and recovered. The residue is filtered and the filtrate evaporated to dryness. Yield, 370 grams sodium dibenzyl sulphanilate.
We do not limit ourselves to the particular chemicals, quantities, times, temperatures, alkalinities or other steps of procedure specifically mentioned as these are given simply as a means for clearly describing our invention.
What we claim is:
1. A process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols of benzyl chloride in the presence of an alkaline earth metal hydroxide.
2. A processfor the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols of benzyl chloride at an alkalinity between pH 7.5 and pH 8.3 in the presence of an alkaline earth metal hydroxide.
3. A process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols of benzyl chloride in the presence of a tertiary aromatic amine.
4. A process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols of benzyl chloride at an alkalinity between pH 7.5 and pH 8.3 in the presence of a tertiary aromatic amine.
5. A process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of slaked lime.
6. A process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of sulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of dimethylaniline.
8. A process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of dimethylaniline at an alkalinity between pH 7.5 and pH 8.3.
9. A process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of pyridine.
10. A process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of pyridine at an alkalinity between pH 7.5 and pH 8.3.
11. A process for the production of dibenzylsulphanilate which comprises reacting in boiling aqueous medium of one mol sulphanilic acid with 2 mols benzylchloride in the presence of mild acid binding agents selected from the group of alkaline earth metal hydroxides, pyridine, and tertiary aromatic amines.
EUGENE A. MARKUSI-l. JOHN J. MALAWISTA. JULIUS MILLER.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US192962A US2208678A (en) | 1938-02-28 | 1938-02-28 | Process for the production of dibenzylsulphanilic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US192962A US2208678A (en) | 1938-02-28 | 1938-02-28 | Process for the production of dibenzylsulphanilic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2208678A true US2208678A (en) | 1940-07-23 |
Family
ID=22711737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US192962A Expired - Lifetime US2208678A (en) | 1938-02-28 | 1938-02-28 | Process for the production of dibenzylsulphanilic acid |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2208678A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2443666A (en) * | 1945-06-21 | 1948-06-22 | Celanese Corp | Process for production of dyestuff comprising condensing 4-sulfo-2-nitro-chlorbenzene with a parasubstituted amine |
-
1938
- 1938-02-28 US US192962A patent/US2208678A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2443666A (en) * | 1945-06-21 | 1948-06-22 | Celanese Corp | Process for production of dyestuff comprising condensing 4-sulfo-2-nitro-chlorbenzene with a parasubstituted amine |
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