CN102344375B - Preparation and synthesis method for 3-aminomethylbenzylamine hydrochloride - Google Patents
Preparation and synthesis method for 3-aminomethylbenzylamine hydrochloride Download PDFInfo
- Publication number
- CN102344375B CN102344375B CN 201110199749 CN201110199749A CN102344375B CN 102344375 B CN102344375 B CN 102344375B CN 201110199749 CN201110199749 CN 201110199749 CN 201110199749 A CN201110199749 A CN 201110199749A CN 102344375 B CN102344375 B CN 102344375B
- Authority
- CN
- China
- Prior art keywords
- hydrochloride
- preparation
- synthesis method
- aminomethylbenzylamine
- amino
- 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 - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000001308 synthesis method Methods 0.000 title abstract 3
- NGAGGLWVRPFBEJ-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine;hydrochloride Chemical compound Cl.NCC1=CC=CC(CN)=C1 NGAGGLWVRPFBEJ-UHFFFAOYSA-N 0.000 title abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 14
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- CWDUIOHBERXKIX-UHFFFAOYSA-K lanthanum(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] CWDUIOHBERXKIX-UHFFFAOYSA-K 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000012047 saturated solution Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- 238000010189 synthetic method Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- AZQPCORTEXNINN-UHFFFAOYSA-N Cl.NCC=1C=C(C=CC1)NC Chemical compound Cl.NCC=1C=C(C=CC1)NC AZQPCORTEXNINN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- -1 compound 3-aminomethyl phenyl methylamine hydrochloride Chemical class 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VEGZHURRCWERMK-UHFFFAOYSA-N benzene-1,3-diamine;hydrochloride Chemical compound Cl.NC1=CC=CC(N)=C1 VEGZHURRCWERMK-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-Phenylethanol Natural products OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 0 [*+]CC1C=CC=C(CN)C1 Chemical compound [*+]CC1C=CC=C(CN)C1 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation and synthesis method for 3-aminomethylbenzylamine hydrochloride. The compound (I) is prepared from meta-xylylene diamine and 3-amino-benzene-amino-benzene hydrochloride and is shown by the following chemical formula in the specification. The synthesis method for the compound comprises synthesis and separation, and is characterized by comprising the following steps: reacting 1mL of meta-xylylene diamine with 0.8933g of lanthanum Chloride hexahydrate for 36 hours in a tetrahydrofuran solution, then, carrying out hot filtering on reaction liquid, and carrying out rotary evaporation on a filtrate, and then, preparing into a saturated solution by using methyl alcohol/petroleum ether; putting in a refrigerator for standing; and separating out a white crystal after one day.
Description
One, technical field
The present invention relates to a kind of preparation and synthetic method of ammonium salt, exactly is a kind of preparation and synthetic method of 3-amino aniline hydrochloride.
Two, background technology
The synthetic method of ammonium salt has many bibliographical informations.As far back as 1956, J.Chem.Soc. reported the synthetic method of some ammonium salts, and nineteen fifty-nine, J.Am.Chem.Soc. has also reported the synthetic method of ammonium salt class.(1.Surrey，Alexander?R.；Lesher，George?Y.；Mayer，J.Richard；Webb，Wm.G.Journal?of?the?American?Chemical?Society(1959)，81?2894-7；2.Davis，M.Journal?of?the?Chemical?Society(1956)，337-43.)。
The applicant does not obtain the target product title complex in the experiment of synthetic m-xylene diamine and Lanthanum trichloride hexahydrate title complex, but obtained another kind of novel cpd 3-amino aniline hydrochloride.
Three, summary of the invention
The present invention aims to provide compound 3-aminomethyl phenyl methylamine hydrochloride, and technical problem to be solved is that one-step synthesis obtains target product.
The alleged a kind of 3-aminomethyl phenyl amine hydrochlorate of the present invention be by the preparation of m-xylene diamine and Lanthanum trichloride hexahydrate by the compound shown in the following chemical formula:
Chemical name: 3-aminomethyl phenyl amine hydrochlorate, be called for short compound (I).
This synthetic method comprises synthesizes and separates, described synthetic m-xylene diamine 1mL and Lanthanum trichloride hexahydrate 0.8933g react 36 hours in tetrahydrofuran solution after, with the reaction solution heat filtering, behind the filtrate rotary evaporation, be mixed with saturated solution with methyl alcohol/sherwood oil, put into refrigerator and leave standstill, separate out white crystal after one day.
This reaction mechanism can be speculated as the methylamino-reactive hydrogen of m-xylene diamine a part and chlorion in tetrahydrofuran solution, shape a part hydrochloric acid rapidly, and become ammonium salt with the aminomethyl of m-xylene diamine.
One step of this synthetic method obtains target product, and technology is simple, and is easy to operate.
Four, description of drawings
Fig. 1 is 3-aminomethyl phenyl amine hydrochlorate
1H NMR.
Fig. 2 is 3-aminomethyl phenyl amine hydrochlorate
13CNMR.
Five, embodiment
1.3-the preparation of aminomethyl phenyl methylamine hydrochloride
At the 100mL round-bottomed flask, with 1mL m-xylene diamine and 0.8933g LaCl
36H
2O is dissolved in the 40mL tetrahydrofuran solution, stirring heating backflow 36h (being white in color).After question response was finished, filtered while hot was spin-dried at Rotary Evaporators in 100 Erlenmeyer flasks, obtains white solid, added a small amount of anhydrous methanol and sherwood oil and joined saturated solution, sealed, and placed refrigerator and cooled but.After one day, bottle wall and bottom adularescent solid generate, and after the filtration, wash with the sherwood oil flushing, vacuumize, and get faint yellow solid, fusing point:＞300 ℃, and results of elemental analyses: theoretical value: C:55.65%; H:7.59%; N:16.23%; Measured value: 55.35%, 7.43%, 15.91%;
1H NMR (300MHz, CDCl
3) 8.446 (s, 1H), 7.39-7.56 (m, 4H), 4.01 (s, 4H).
13CNMR (75MHz, CDCl
3) 134.46,129.67,128.98,128.78,128.57,42.1.IR (KBr compressing tablet): 3346,2868,1464,1324,941,597.
2. the nitrile silicification reaction is used
The preparation of 2-phenyl-2-(three silyloxies) propionitrile
0.0314g (0.15mmol) hydrochloride compound (I) is inserted the round-bottomed flask of 25ml, add 2ml tetrahydrofuran (THF), 0.1ml phenyl aldehyde (1mmol) and 0.3ml trimethyl silicane nitrile, stirring at room 8 hours is carried out reaction solution
1H NMR test.Phenyl aldehyde 0.1mL, TMSCN 0.3ml (3.3mmol) add down at 20～30 ℃ in succession, behind the 120h, behind column chromatography (sherwood oil/methylene dichloride: 5/1), get colourless oil liquid, transformation efficiency: 15.0%,
1H NMR (300MHz, CDCl
3) 7.56-7.59 (m, 0.9Hz, 2H), 7.31-7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H).
13C NMR (75MHz, CDCl
3) 136.1,128.8 (x2), 126.2 (x2), 119.1,63.5 ,-0.39 (x3).
3. Henle reaction is used
The preparation of 2-nitro-1 phenylethyl alcohol
0.0314g (0.15mmol) 3-aminomethyl phenyl methylamine hydrochloride compound (I) is inserted the round-bottomed flask of 25mL, add 2ml anhydrous methanol, 0.1ml phenyl aldehyde (1mmol) and 0.5ml Nitromethane 99Min., stirring at room 72 hours is carried out reaction solution
1H NMR test.Transformation efficiency: 90.1%.
1HNMR(300MHz，CDCl
3)7.28～7.32(m，5H，Ar-H)，5.32～5.35(d，J＝9.18Hz，1H，-CH)，4.38～4.56(m，2H，-CH
2)，3.89(br，1H，-OH).
Claims (1)
1. one kind by the 3-aminomethyl phenyl methylamine hydrochloride synthetic method shown in the following chemical formula, comprise and synthesize and separate, after it is characterized in that m-xylene diamine 1mL and Lanthanum trichloride hexahydrate 0.8933g react 36 hours in tetrahydrofuran solution, with the reaction solution heat filtering, behind the filtrate rotary evaporation, be mixed with saturated solution with methyl alcohol/sherwood oil, put into refrigerator and leave standstill, separate out white crystal after one day
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110199749 CN102344375B (en) | 2011-07-18 | 2011-07-18 | Preparation and synthesis method for 3-aminomethylbenzylamine hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110199749 CN102344375B (en) | 2011-07-18 | 2011-07-18 | Preparation and synthesis method for 3-aminomethylbenzylamine hydrochloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102344375A CN102344375A (en) | 2012-02-08 |
| CN102344375B true CN102344375B (en) | 2013-07-03 |
Family
ID=45543493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110199749 Expired - Fee Related CN102344375B (en) | 2011-07-18 | 2011-07-18 | Preparation and synthesis method for 3-aminomethylbenzylamine hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102344375B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788330B (en) * | 2015-03-25 | 2017-03-22 | 合肥工业大学 | Preparation method and synthesis method of chiral double L-leucine hydrochloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310924A (en) * | 1993-04-30 | 1994-05-10 | E. I. Du Pont De Nemours And Company | Process for preparing thiabendazole |
| CN101774928A (en) * | 2010-02-10 | 2010-07-14 | 烟台万华聚氨酯股份有限公司 | Method for preparing m-xylylenediamine |
| CN101891688A (en) * | 2010-07-30 | 2010-11-24 | 孝感市诚嘉药物研究所 | Preparation method for bendazol in industrialized production |
-
2011
- 2011-07-18 CN CN 201110199749 patent/CN102344375B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310924A (en) * | 1993-04-30 | 1994-05-10 | E. I. Du Pont De Nemours And Company | Process for preparing thiabendazole |
| CN101774928A (en) * | 2010-02-10 | 2010-07-14 | 烟台万华聚氨酯股份有限公司 | Method for preparing m-xylylenediamine |
| CN101891688A (en) * | 2010-07-30 | 2010-11-24 | 孝感市诚嘉药物研究所 | Preparation method for bendazol in industrialized production |
Non-Patent Citations (2)
| Title |
|---|
| M.DAVIS.New Trypanocides. Part I. Quaternary Salts derived from. 2 : 7-Diaminophenanthridine and the Attempted Preparation of Quaternary Xalts from 2 : 7 - Diamino-9-anilinophenanthridine.《Journal of the American Chemistry Society》.1956,337-343页. |
| M.DAVIS.New Trypanocides. Part I. Quaternary Salts derived from. 2 : 7-Diaminophenanthridine and the Attempted Preparation of Quaternary Xalts from 2 : 7- Diamino-9-anilinophenanthridine.《Journal of the American Chemistry Society》.1956,337-343页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102344375A (en) | 2012-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106365986B (en) | Compound and preparation method thereof and the purposes in synthesis Bu Waxitan | |
| CN103772278A (en) | Important tetrahydroisoquinoline derivative midbody and synthesis method thereof | |
| CN104530106A (en) | Method for preparing arylboronic acid compound | |
| CN101219997A (en) | Synthesis of 2-chlorine-5- amido pyrimidine | |
| CN102344375B (en) | Preparation and synthesis method for 3-aminomethylbenzylamine hydrochloride | |
| CN101973891B (en) | Preparation of chiral (S)-alpha-phenylethylamine hydrochloride and synthesis method thereof | |
| CN101857559A (en) | Chiral α-(trichloromethyl)amine compound and preparation method thereof | |
| CN105037442B (en) | Chiral thioether-phosphine ligand and its preparation method and use | |
| CN103275108B (en) | Preparation and synthesis method of chiral copper complex | |
| CN102675152A (en) | Preparation method of intermediate glycol of antidepressant citalopram | |
| CN105237413B (en) | Chiral crystal-water-containing phenylglycinol cobalt complex | |
| CN101973889B (en) | Method for preparing and synthesizing chiral (R)-alpha-phenethylamine hydrochloride | |
| CN102206159B (en) | Preparation method and synthesizing method of alpha-phenylethylamine acetate | |
| CN102516236B (en) | Preparation method of antipsychotic drug iloperidone | |
| CN102329240A (en) | Method for preparing and synthesizing m-xylylenediamine dihydrochloride | |
| CN102627571B (en) | Preparation and synthesis method for chiral ammonium salt | |
| CN102206160B (en) | Preparation and synthesis method for 2-aminophenylamine hydrochloride | |
| KR101264166B1 (en) | Method for preparing 1,2-bis(5-aminotetrazol-1-yl)ethane | |
| CN102304151A (en) | Manganese complex and synthesis method thereof | |
| JP2010120926A (en) | Polycyclic pentafluorosulfanylbenzene compound and method for producing the same | |
| CN107417489B (en) | Method for synthesizing bromo-fused ring aromatic compound | |
| Komatsuzaki et al. | An Anion Receptor Based on Poly-Substituted Cobalticinium Complexes. | |
| KR20130071232A (en) | Method for preparation of tetrahydroquinoline derivatives | |
| CN105153211B (en) | Method for synthesis of 1-(N-Boc-4-piperidine)-4-pyrazoleboronic acid pinaol ester | |
| WO2015163446A1 (en) | Method for producing imidazole compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130703 Termination date: 20140718 |
|
| EXPY | Termination of patent right or utility model |