CN103012154B - Method for preparing organic amine through benzsulfamide derivative ammonolysis - Google Patents
Method for preparing organic amine through benzsulfamide derivative ammonolysis Download PDFInfo
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- CN103012154B CN103012154B CN201210551285.9A CN201210551285A CN103012154B CN 103012154 B CN103012154 B CN 103012154B CN 201210551285 A CN201210551285 A CN 201210551285A CN 103012154 B CN103012154 B CN 103012154B
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- Prior art keywords
- organic amine
- reaction
- formula
- benzenesulfonamide derivatives
- ammonium chloride
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- 150000001412 amines Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000005915 ammonolysis reaction Methods 0.000 title abstract 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 13
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 150000008331 benzenesulfonamides Chemical class 0.000 claims description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 5
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical group NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical group CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-butylamine Natural products CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical group CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical group NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical group CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 substituent benzenesulfonamide derivatives Chemical class 0.000 description 2
- 101100493820 Caenorhabditis elegans best-1 gene Proteins 0.000 description 1
- YDVIYKMHWFHKMM-UHFFFAOYSA-N N.C(CCC)NS(=O)(=O)C1=CC=CC=C1 Chemical compound N.C(CCC)NS(=O)(=O)C1=CC=CC=C1 YDVIYKMHWFHKMM-UHFFFAOYSA-N 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000013462 industrial intermediate Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- XRTYMJYAOZHUHI-UHFFFAOYSA-N n-(2-methylpropyl)benzenesulfonamide Chemical compound CC(C)CNS(=O)(=O)C1=CC=CC=C1 XRTYMJYAOZHUHI-UHFFFAOYSA-N 0.000 description 1
- YRJGYGPIEHIQPP-UHFFFAOYSA-N n-cyclohexylbenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NC1CCCCC1 YRJGYGPIEHIQPP-UHFFFAOYSA-N 0.000 description 1
- QKIWHADSHFVRFN-UHFFFAOYSA-N n-propan-2-ylbenzenesulfonamide Chemical compound CC(C)NS(=O)(=O)C1=CC=CC=C1 QKIWHADSHFVRFN-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing organic amine through benzsulfamide derivative ammonolysis. Benzsulfamide derivative shown in formula I and ammonium chloride are catalyzed by phosphomolybdic acid and react in a solvent, and hydrogen is utilized to regulate the reaction pressure; the molar ratio of benzsulfamide derivative to both ammonium chloride and phosphomolybdic acid is 1:1-3:(0.01-0.05), the reaction pressure is 0.2-1MPa, the reaction temperature is 30 DEG C-90 DEG C, and the reaction time is 7-10 hours; after the reaction, sodium hydroxide is added to the liquid reactant, the mixture is stirred and filtered to obtain a filtrate, the filtrate is distilled to acquire organic amine shown in formula I; the molar ratio of sodium hydroxide to ammonium chloride is 1:(0.95-1.05); R-NH2 and the formula II is shown in the specification.
Description
Technical field
The present invention relates to a kind of method of being prepared organic amine by benzenesulfonamide derivatives ammonia solution.
Background technology
Containing the substituent benzenesulfonamide derivatives of N, be a kind of industrial chemicals and intermediate; can be made by benzsulfamide and halohydrocarbons reaction; electron attraction due to alkylsulfonyl; its intramolecular N-hydrocarbon key is compared with easy fracture; having document (Synlett, (11): 1901-1904,2004) to report with N-styroyl benzsulfamide reacts at normal temperatures with Periodic acid; the bond rupture of N-styroyl be can make, benzsulfamide and methyl phenyl ketone generated.If can make can generate corresponding organic amine after the bond rupture of N-hydrocarbon, this reacts just highly significant, because the organic amine by product of preparation seldom thus, separating-purifying is convenient.But the report that not yet has N-hydrocarbon bond rupture generation organic amine in the substituent benzenesulfonamide derivatives of N at present.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of technique is succinct, reaction temperature and, benzenesulfonamide derivatives ammonia solution that yield is higher prepares the method for organic amine.
In order to solve the problems of the technologies described above, the invention provides a kind of method of being prepared organic amine by benzenesulfonamide derivatives ammonia solution, by the benzenesulfonamide derivatives shown in formula II with ammonium chloride under the catalysis of phospho-molybdic acid, react in solvent, utilize hydrogen to regulate reaction pressure;
The mol ratio of benzenesulfonamide derivatives and ammonium chloride, phospho-molybdic acid is 1:1 ~ 3:0.01 ~ 0.05, and reaction pressure is 0.2 ~ 1MPa, and temperature of reaction is 30 ~ 90 ℃, and the reaction times is 7 ~ 10 hours;
After reaction finishes, in reaction solution, add sodium hydroxide, stir, filter, gained filtrate distillation (for underpressure distillation or air distillation), obtains the organic amine shown in formula I; The mol ratio of sodium hydroxide and ammonium chloride is the best 1:1 of being of 1:0.95 ~ 1.05();
Formula I formula II
In formula I, R is butyl, sec.-propyl, styroyl, isobutyl-or cyclohexyl.
As the improvement of being prepared the method for organic amine by benzenesulfonamide derivatives ammonia solution of the present invention:
When benzenesulfonamide derivatives is N-butylbenzenesulfonamide, organic amine is butylamine;
When benzenesulfonamide derivatives is N-isopropyl benzene sulphonamide, organic amine is Isopropylamine;
When benzenesulfonamide derivatives is N-styroyl benzsulfamide, organic amine is phenylethylamine (that is, 2-phenylethylamine);
When benzenesulfonamide derivatives is N-isobutyl-benzene sulphonamide, organic amine is sec-butylamine;
When benzenesulfonamide derivatives is N-cyclohexyl benzene sulfonamide, organic amine is hexahydroaniline.
As the further improvements in methods of being prepared organic amine by benzenesulfonamide derivatives ammonia solution of the present invention: solvent is Isosorbide-5-Nitrae-dioxane.
As the further improvements in methods of being prepared organic amine by benzenesulfonamide derivatives ammonia solution of the present invention: solvent is 2 ~ 5mL/1g with the volume/mass ratio of the benzenesulfonamide derivatives shown in formula II.
Remarks explanation: in step 1) of the present invention, be preferably: the mol ratio of benzenesulfonamide derivatives and ammonium chloride, phospho-molybdic acid is 1:1 ~ 2:0.01 ~ 0.02, reaction pressure is 0.5 ~ 0.7MPa, and temperature of reaction is 70 ~ 90 ℃, and the reaction times is 7 ~ 10 hours.
Benzenesulfonamide derivatives ammonia solution of the present invention is prepared the method for organic amine, and reaction process is simple to operate, and temperature of reaction is lower, convenient post-treatment, and yield is higher simultaneously.
Embodiment
Embodiment 1, N-butylbenzenesulfonamide ammonia solution are prepared butylamine
In autoclave, add 0.2mol N-butylbenzenesulfonamide (42.6g), 0.22mol ammonium chloride (12g), 5.5g(0.003mol) phospho-molybdic acid and 130mL 1,4-dioxane, to pass into hydrogen to 0.5MPa after air in nitrogen replacement still, be warming up to 80 ℃ of stirring reactions finishes for 8 hours, to adding in reaction solution with the sodium hydroxide of ammonium chloride equimolar amount and stirring, filter, decompression (0.05MPa) distillation filtrate, collects the cut of 30 ~ 40 ℃, obtain butylamine 11.4g, yield is 78%.
Embodiment 2 ~ 5:
Change kind (molar weight is constant), the ammonium chloride add-on (being called for short R1), 1 of the benzenesulfonamide derivatives in embodiment 1,4-dioxane add-on (being called for short V1), phospho-molybdic acid add-on (being called for short C1), reaction pressure (being called for short P), temperature of reaction (being called for short T) and the reaction times (being called for short t) of utilizing hydrogen to regulate, the yield that obtains corresponding organic amine is Y.Detailed data is in Table 1.
Table 1
Remarks explanation:
In embodiment 2, air distillation, collects the cut of 32 ~ 34 ℃, and products therefrom is Isopropylamine;
In embodiment 3, underpressure distillation, collects the cut of 80 ~ 90 ℃, and products therefrom is phenylethylamine;
In embodiment 4, underpressure distillation, collects the cut of 28 ~ 38 ℃, and products therefrom is isobutylamine;
In embodiment 5, underpressure distillation, collects the cut of 50 ~ 60 ℃, and products therefrom is hexahydroaniline.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (2)
1. by benzenesulfonamide derivatives ammonia solution, prepared the method for organic amine, it is characterized by: by the benzenesulfonamide derivatives shown in formula II with ammonium chloride under the catalysis of phospho-molybdic acid, react in solvent, utilize hydrogen to regulate reaction pressure;
The mol ratio of described benzenesulfonamide derivatives and ammonium chloride, phospho-molybdic acid is 1:1～3:0.01～0.05, and reaction pressure is 0.2～1MPa, and temperature of reaction is 30～90 ℃, and the reaction times is 7～10 hours; Described solvent is Isosorbide-5-Nitrae-dioxane;
After reaction finishes, in reaction solution, add sodium hydroxide, stir, filter, the distillation of gained filtrate, obtains the organic amine shown in formula I; The mol ratio of described sodium hydroxide and ammonium chloride is 1:0.95～1.05;
In formula I, R is butyl, sec.-propyl, styroyl, isobutyl-or cyclohexyl.
2. the method for being prepared organic amine by benzenesulfonamide derivatives ammonia solution according to claim 1, is characterized in that: solvent is 2～5mL/1g with the volume/mass ratio of the benzenesulfonamide derivatives shown in formula II.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210551285.9A CN103012154B (en) | 2012-12-18 | 2012-12-18 | Method for preparing organic amine through benzsulfamide derivative ammonolysis |
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| CN201210551285.9A CN103012154B (en) | 2012-12-18 | 2012-12-18 | Method for preparing organic amine through benzsulfamide derivative ammonolysis |
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| Publication Number | Publication Date |
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| CN103012154A CN103012154A (en) | 2013-04-03 |
| CN103012154B true CN103012154B (en) | 2014-10-08 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196046A (en) * | 1995-09-15 | 1998-10-14 | 巴斯福股份公司 | Separation of optically active amides |
| CN1446792A (en) * | 2002-03-21 | 2003-10-08 | 庞仁杰 | technique for producing tert-tutylamine |
| US6713652B1 (en) * | 1999-03-24 | 2004-03-30 | Basf Aktiengesellschaft | Process for hydrolyzing optically active amides |
| CN101134738A (en) * | 2007-09-29 | 2008-03-05 | 暨南大学 | Asymmetric synthesis method of (S)-rivastigmine |
| CN102320981A (en) * | 2011-07-19 | 2012-01-18 | 上海泰坦化学有限公司 | Chiral intermediate (S)-1-cyclobutyl ethylamine hydrochloride as well as preparation method and application thereof |
-
2012
- 2012-12-18 CN CN201210551285.9A patent/CN103012154B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196046A (en) * | 1995-09-15 | 1998-10-14 | 巴斯福股份公司 | Separation of optically active amides |
| US6713652B1 (en) * | 1999-03-24 | 2004-03-30 | Basf Aktiengesellschaft | Process for hydrolyzing optically active amides |
| CN1446792A (en) * | 2002-03-21 | 2003-10-08 | 庞仁杰 | technique for producing tert-tutylamine |
| CN101134738A (en) * | 2007-09-29 | 2008-03-05 | 暨南大学 | Asymmetric synthesis method of (S)-rivastigmine |
| CN102320981A (en) * | 2011-07-19 | 2012-01-18 | 上海泰坦化学有限公司 | Chiral intermediate (S)-1-cyclobutyl ethylamine hydrochloride as well as preparation method and application thereof |
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| CN103012154A (en) | 2013-04-03 |
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