US2979503A - Process for producing certain 2-aminophenoldisulfonamides - Google Patents
Process for producing certain 2-aminophenoldisulfonamides Download PDFInfo
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- US2979503A US2979503A US704241A US70424157A US2979503A US 2979503 A US2979503 A US 2979503A US 704241 A US704241 A US 704241A US 70424157 A US70424157 A US 70424157A US 2979503 A US2979503 A US 2979503A
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- ethylamine
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- benzoxazolone
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- aminophenoldisulfonamides
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- 238000000034 method Methods 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 26
- ASSKVPFEZFQQNQ-UHFFFAOYSA-N 2-benzoxazolinone Chemical compound C1=CC=C2OC(O)=NC2=C1 ASSKVPFEZFQQNQ-UHFFFAOYSA-N 0.000 description 23
- -1 methoxy, ethoxy Chemical group 0.000 description 10
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 8
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 7
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000002862 amidating effect Effects 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C09B39/00—Other azo dyes prepared by diazotising and coupling
Definitions
- This invention relates to novel compounds and to novel methods for producing same. More particularly, the compounds of the instant invention are Z-aminophenoldisulfonamides having the formula:
- R and R are'selected from the group consisting of H, alkyl, aralkyl, cycloalkyl, and aryl, and when taken together, the atoms necessary to form a heterocycle.
- the compounds of the instant invention have been found to be highly effective as diazo components in the production of metallizible azo dyestuffs, asdisclosed and claimed in our copending application Serial No. 104,312, filed on even date herewith.
- R and R may be the same or different, and may be H, alkyl such as octadecyl, decyl, and preferably lower alkyl such as methyl, ethyl, propyl, isobutyl and hexyl, cycloalkyl such as cyclohexyl, aralkyl such as benzyl, aryl such as phenyl and biphenyl, and when taken together, morpholinyl, piperidinyl, pyridyl, and the like. It will be understood that 'R and R as above defined may contain inert substituents such as hydroxy, lower alkoxy such as methoxy, ethoxy, and the like.
- the process of the instant invention for producing the above defined compounds comprises heating one mole of benzoxazolone with a minimum of about 4 up to about 12 moles of chlorosulfonic acid at a temperature of about 90 to 120 C. for about 3 to hours, treating the resulting benzoxazolone disulfonylchloride with at least 4 moles of a compound of the formula R R NH, wherein R 'and R have the values given above, and then subjecting the resulting benzoxazolone disulfonamide to aqueous alkaline hydrolysis conditions.
- the benzoxazolone and chlorosulfonic acid are preferably admixed at a low temperature, i.e. less than about 10 C., and the temperature slowly raised and maintained at a temperature of 90 to 120 C. for sufficient time to complete the reaction, usually from about 3 to 10 hours. Temperatures above 10 C. and up to 120 C. may be employed for the initial admixture step, but are not preferred since thechlorosulfonic acid is more difficult to work at higher temperatures.
- ammonium hydroxide ammonium carbonate
- ethanolamine diethanolamine
- benzylamine methylbenzylamine, cyclohexylamine, aniline, toluidine, xylidine, anisidine, morpholine, piperidine, pyridine, and the lke.
- this amidating step may be carried out be tween the disulfonylchloride and the amidating compound alone or in aqueous or organic solvent solution or dispersion at temperatures ranging from about 5 to 30 C. for periods ranging from about 1 to 24 hours. Concentrated solutions of the ammonia or amine compound are preferred, but such concentrations may range from about 30 to 100% by weight of said compound.
- compatible solvents which are inert under thev conditions of amidation, there may be mentioned chlorobenzene, trichlorobenzene, nitrobenzene, toluene, dioxane, carbon tetrachloride, ether and the like.
- the disulfonamide Upon completion of the amidating reaction, the disulfonamide is filtered and sucked dry. It has the formula sis conditions to produce the desired 2-arninophenoldiually employing about a 15 to- 35% by volume caustic soda solution using a minimum of two equivalents of caustic up to about 300% of theory.
- Other alkaline substances may be employed, as for example, potassium hydroxide and the like.
- elevated temperatures usually at or near the boil, for sufficient time to open the benzoxazolone ring, usually from about 1 to 10 hours.
- the hydrolysis medium is then neutralized with acid, for example by acidification to Congo acid followed by cooling, filtering and washing.
- Example 1 Charge to a 500 cc. 3-neck flask fitted with an agitator and thermometer, 350 g. chlorosulfonic acid. Cool to 5 C. Add 50 g. 100% benzoxazolone dry at such a rate that the temperature does not exceed 10 C.
- the ethylamine may be replaced by'ammoniurn hydroxide, methyl amine, dimethylamine, ethylamine, diethylamine, propylamine, isob-utylamine, ethanolamine, diethanolamine, propanolamine, methylethanolamine, benzylamine, methylhenzylamine, cyclohexylamine, ammonium carbonate, morpholine, piperi-. dine, pyridine and, the like, as exemplified by the followingexamples,
- Example 2 7 Example 1 is repeated but substituting for the ethyl: amine, the same amount of dimethylamine.
- Theproduct has the structure
- Example 3 Example 1 is repeated but substituting for the ethylamine, 95 g. ethanolamine.
- the product has the structure
- Example 4 Example 1 is repeated but substituting for the ethylamine, 153 g. 'cyclohexylamine.
- the product has the formula [HUCAHNO :Sh:
- Example 5 Example 1, isrepeated but substitutingfor the ethylamine, 135 g. morpholine.
- the product has theformula Ex mpl fil Example 1 is repeated but substituting for the ethylamine, 102 cc. NH OH 29' Be;
- the product-hasthe formula Example 7 Example 1 is repeated but substituting for the; ethylamine, 140 g. aniline.
- the product has the formula lg lfs I
- Example 8 Example 1 is repeated; but substituting for the ethylamine, 160 g. benzylamine.
- the product has the formula NH; [O-cmrmms]
- Example 9 Example 1 is repeated but substituting forthe ethylamine, 128 g. piperidine.
- a process for producing a compound having the formula wherein R and'IR are selected from the group consisting of H, alkyl, aralkyl, cycloalkyl, and aryl, and when taken together, the atoms necessary to form a heterocycle, comprising heating one mole of benzoxazolone with at least about 4 up to about 12 moles of chlorosulfonic acid at a temperature of about to C.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
PROCESS FOR PRODUCING CERTAIN Z-AMINO- PHENOLDISULFONAMIDES William H. Armento, Albany, and William E. Wallace, Rensselaer, N.Y., assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Dec. 23, 1957, Ser. No. 704,241
6 Claims. c1. zen-241.1
This invention relates to novel compounds and to novel methods for producing same. More particularly, the compounds of the instant invention are Z-aminophenoldisulfonamides having the formula:
wherein R and R are'selected from the group consisting of H, alkyl, aralkyl, cycloalkyl, and aryl, and when taken together, the atoms necessary to form a heterocycle. The compounds of the instant invention have been found to be highly effective as diazo components in the production of metallizible azo dyestuffs, asdisclosed and claimed in our copending application Serial No. 104,312, filed on even date herewith.
In the above formula, R and R may be the same or different, and may be H, alkyl such as octadecyl, decyl, and preferably lower alkyl such as methyl, ethyl, propyl, isobutyl and hexyl, cycloalkyl such as cyclohexyl, aralkyl such as benzyl, aryl such as phenyl and biphenyl, and when taken together, morpholinyl, piperidinyl, pyridyl, and the like. It will be understood that 'R and R as above defined may contain inert substituents such as hydroxy, lower alkoxy such as methoxy, ethoxy, and the like.
The process of the instant invention for producing the above defined compounds comprises heating one mole of benzoxazolone with a minimum of about 4 up to about 12 moles of chlorosulfonic acid at a temperature of about 90 to 120 C. for about 3 to hours, treating the resulting benzoxazolone disulfonylchloride with at least 4 moles of a compound of the formula R R NH, wherein R 'and R have the values given above, and then subjecting the resulting benzoxazolone disulfonamide to aqueous alkaline hydrolysis conditions.
In carrying out the first step of the instant process, the benzoxazolone and chlorosulfonic acid are preferably admixed at a low temperature, i.e. less than about 10 C., and the temperature slowly raised and maintained at a temperature of 90 to 120 C. for sufficient time to complete the reaction, usually from about 3 to 10 hours. Temperatures above 10 C. and up to 120 C. may be employed for the initial admixture step, but are not preferred since thechlorosulfonic acid is more difficult to work at higher temperatures. Since this initial reaction probably proceeds in two stages, in the first of which the benzoxazolone disulfonic acid is first formed, and in the second of which the disulfonic acid reacts with two more moles of chlorosulfonic acid, 4 moles of chlorosulfonic acid are theoretically required to form the benzoxazolone disulfonylchloride, having the formula o----co NH (SOzCD However, an amount in excess of this theoretical amount,
- .up to about- 12'moles of the chlorosulfonic acid per mole of the benzoxazolone is preferred to prevent formation of undesirable by-products.
Reaction of the disulfonyl chloride with ammonia or an amine toproduce the corresponding disulfonamide is readily carried out at ordinary temperatures by mere admixture. Here again, 4 moles of the amidating compound of the formula R R NH are theoretically required for each mole of the disulfonylchloride, although it is preferred to employ an excess of up to about 14 moles for neutralization of acidic substances and thelike. As representative of suitable compounds for this amidation there may be mentioned ammonium hydroxide, ammonium carbonate; methylamine, ethylamine,methylethyl amine,'diethylamine, dimethylatnine, propylamine, isobutylamine, ethanolamine, diethanolamine, "propanol amine, hexylamine, decylamine, octadecylamine, methylethanolamine, benzylamine, methylbenzylamine, cyclohexylamine, aniline, toluidine, xylidine, anisidine, morpholine, piperidine, pyridine, and the lke.
'In general, this amidating step may be carried out be tween the disulfonylchloride and the amidating compound alone or in aqueous or organic solvent solution or dispersion at temperatures ranging from about 5 to 30 C. for periods ranging from about 1 to 24 hours. Concentrated solutions of the ammonia or amine compound are preferred, but such concentrations may range from about 30 to 100% by weight of said compound. As compatible solvents which are inert under thev conditions of amidation, there may be mentioned chlorobenzene, trichlorobenzene, nitrobenzene, toluene, dioxane, carbon tetrachloride, ether and the like. Upon completion of the amidating reaction, the disulfonamide is filtered and sucked dry. It has the formula sis conditions to produce the desired 2-arninophenoldiually employing about a 15 to- 35% by volume caustic soda solution using a minimum of two equivalents of caustic up to about 300% of theory. Other alkaline substances may be employed, as for example, potassium hydroxide and the like. elevated temperatures, usually at or near the boil, for sufficient time to open the benzoxazolone ring, usually from about 1 to 10 hours. The hydrolysis medium is then neutralized with acid, for example by acidification to Congo acid followed by cooling, filtering and washing. The following examples, in which parts are by weight unless otherwise indicated are illustrative of the instant invention and are not to be regarded as limitative.
Example 1 Charge to a 500 cc. 3-neck flask fitted with an agitator and thermometer, 350 g. chlorosulfonic acid. Cool to 5 C. Add 50 g. 100% benzoxazolone dry at such a rate that the temperature does not exceed 10 C.
Allow to warm during 1 hour to room temperature.
Heat to l00-110 C. during 1 hour and hold at that temperature for 4 to 5 hours. Cool to room temperature and pour onto crushed ice. Filter and wash with ice water until almost neutral to Congo paper. Add the paste to an aqueous solution of ethylamine containing g. of ethylamine which is kept below 10 C. during Patented Apr. 11, 1961 The hydrolysis is carried out at- I aemroa In the above example, the ethylamine may be replaced by'ammoniurn hydroxide, methyl amine, dimethylamine, ethylamine, diethylamine, propylamine, isob-utylamine, ethanolamine, diethanolamine, propanolamine, methylethanolamine, benzylamine, methylhenzylamine, cyclohexylamine, ammonium carbonate, morpholine, piperi-. dine, pyridine and, the like, as exemplified by the followingexamples,
Example 2 7 Example 1 is repeated but substituting for the ethyl: amine, the same amount of dimethylamine. Theproduct has the structure Example 3 Example 1 is repeated but substituting for the ethylamine, 95 g. ethanolamine. The product has the structure Example 4 Example 1 is repeated but substituting for the ethylamine, 153 g. 'cyclohexylamine. The product has the formula [HUCAHNO :Sh:
Example 5 Example 1, isrepeated but substitutingfor the ethylamine, 135 g. morpholine. The product has theformula Ex mpl fil Example 1 is repeated but substituting for the ethylamine, 102 cc. NH OH 29' Be; The product-hasthe formula Example 7 Example 1 is repeated but substituting for the; ethylamine, 140 g. aniline. The product has the formula lg lfs I Example 8 Example 1 is repeated; but substituting for the ethylamine, 160 g. benzylamine. The product has the formula NH; [O-cmrmms] Example 9 Example 1 is repeated but substituting forthe ethylamine, 128 g. piperidine. The product has the formula This invention has been disclosed with respect to cer tain preferred embodiments, and there will become obvious to persons skilled in the art various modifications; equivalents or variations thereof which are intended to be included within the spirit and scope of this invention.
We claim:
1, A process for producing a compound having the formula wherein R and'IR are selected from the group consisting of H, alkyl, aralkyl, cycloalkyl, and aryl, and when taken together, the atoms necessary to form a heterocycle, comprising heating one mole of benzoxazolone with at least about 4 up to about 12 moles of chlorosulfonic acid at a temperature of about to C. for about 3 to 10 hours, treating the resulting benzoxazolone disulfonylchloride with at least 4 moles of an amine compound of the formula R R NH wherein R, and R are selected from the group consisting of H, alkyl, aralkyl, cycloalkyl, and aryl, and when taken together, the atoms necessary to complete a heterocycle, and then subjecting the resulting benzoxazolone disulfonamide to aqueous alkaline hydrolysis conditions.
2. A process as defined in claim 1 wherein said amine compound is ethylamine.
3. A process as defined in claim 1 wherein said amine compound is dimethylamine.
4. A process as defined in claim 1 wherein said amine compound is cyclohexylamine.
5. A process as defined in claim 1 wherein said amine compound is morpholine.
6. A process as defined in claiml wherein said amine compound is ammonia.
References Cited in the file of this patent UNITED STATES PATENTS Schetty et a1. Dec. 24, 1957 Strobei et a1. May 13, 1958 OTHER REFERENCES 5 Scudi et al.: J. Amer. Chem. Soc., vol. 63, page 879 Elderfield: .Heterocyclic Compounds, vol. 5, pages Migrdichian: Organic Synthesis, vol. 2, pages 1688, 10 1690-1 (1957).
Claims (1)
1. A PROCESS FOR PRODUCING A COMPOUND HAVING THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US704241A US2979503A (en) | 1957-12-23 | 1957-12-23 | Process for producing certain 2-aminophenoldisulfonamides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US704241A US2979503A (en) | 1957-12-23 | 1957-12-23 | Process for producing certain 2-aminophenoldisulfonamides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2979503A true US2979503A (en) | 1961-04-11 |
Family
ID=24828678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US704241A Expired - Lifetime US2979503A (en) | 1957-12-23 | 1957-12-23 | Process for producing certain 2-aminophenoldisulfonamides |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2979503A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3066156A (en) * | 1960-01-04 | 1962-11-27 | Merck & Co Inc | Novel method for preparing disulfamylaniline compounds |
| US3078267A (en) * | 1960-12-20 | 1963-02-19 | Gen Aniline & Film Corp | Metallized azo dyes containing a 2-aminophenoldisulfonamide diazo component |
| US3139429A (en) * | 1960-10-14 | 1964-06-30 | Ciba Ltd | Vat dyestuffs of the dibenzanthrone series |
| US3153642A (en) * | 1959-12-22 | 1964-10-20 | Carbochimique Sa | Azo dyestuffs containing a beta-cyanoethyl, alkyl amino sulfonyl group |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2202219A (en) * | 1937-03-04 | 1940-05-28 | Winthrop Chem Co Inc | Substituted sulphanilamides and process for making them |
| US2333445A (en) * | 1941-08-14 | 1943-11-02 | American Cyanamid Co | Hydroxyaminobenzenesulphonamides |
| US2727031A (en) * | 1951-08-07 | 1955-12-13 | Ciba Ltd | Metalliferous pyrazolone azodyestuffs |
| US2804454A (en) * | 1954-07-14 | 1957-08-27 | Geigy Ag J R | Complex heavy metal compounds of monoazo dyestuffs |
| US2809194A (en) * | 1957-10-08 | Thiadiazine type natriuretic agents | ||
| US2817655A (en) * | 1952-09-10 | 1957-12-24 | Geigy Ag J R | Azo dyestuffs containing heavy metal |
| US2834772A (en) * | 1954-08-20 | 1958-05-13 | Gen Aniline & Film Corp | Metallized compounds of 3-amino-4-hydroxybenzene sulfonylmorpholine azo dyestuffs |
-
1957
- 1957-12-23 US US704241A patent/US2979503A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2809194A (en) * | 1957-10-08 | Thiadiazine type natriuretic agents | ||
| US2202219A (en) * | 1937-03-04 | 1940-05-28 | Winthrop Chem Co Inc | Substituted sulphanilamides and process for making them |
| US2333445A (en) * | 1941-08-14 | 1943-11-02 | American Cyanamid Co | Hydroxyaminobenzenesulphonamides |
| US2727031A (en) * | 1951-08-07 | 1955-12-13 | Ciba Ltd | Metalliferous pyrazolone azodyestuffs |
| US2817655A (en) * | 1952-09-10 | 1957-12-24 | Geigy Ag J R | Azo dyestuffs containing heavy metal |
| US2804454A (en) * | 1954-07-14 | 1957-08-27 | Geigy Ag J R | Complex heavy metal compounds of monoazo dyestuffs |
| US2834772A (en) * | 1954-08-20 | 1958-05-13 | Gen Aniline & Film Corp | Metallized compounds of 3-amino-4-hydroxybenzene sulfonylmorpholine azo dyestuffs |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3153642A (en) * | 1959-12-22 | 1964-10-20 | Carbochimique Sa | Azo dyestuffs containing a beta-cyanoethyl, alkyl amino sulfonyl group |
| US3066156A (en) * | 1960-01-04 | 1962-11-27 | Merck & Co Inc | Novel method for preparing disulfamylaniline compounds |
| US3139429A (en) * | 1960-10-14 | 1964-06-30 | Ciba Ltd | Vat dyestuffs of the dibenzanthrone series |
| US3078267A (en) * | 1960-12-20 | 1963-02-19 | Gen Aniline & Film Corp | Metallized azo dyes containing a 2-aminophenoldisulfonamide diazo component |
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