CN105218380A - The preparation method of one (±)-1,2-diphenyl ethylene diamine - Google Patents
The preparation method of one (±)-1,2-diphenyl ethylene diamine Download PDFInfo
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Abstract
The invention discloses the preparation method of one (±)-1,2-diphenyl ethylene diamine.Adopt 1,2-diphenylthanedione dioxime, with hydrazine hydrate, formic acid, sodium formiate, ammonium formiate, the one in ammonium formiate-triethylamine system is hydrogen source, at 20 DEG C-100 DEG C, employing Raney's nickel is catalyzer, gac is promotor, and in polar solvent, catalytic reduction obtains (±)-1,2-diphenyl ethylene diamine.Raw material sources of the present invention are simply extensive, inexpensive, production technique safety, and technical process is short, and reaction conditions is gentle, and cost is low, advantages of environment protection, are very applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to the preparation method of one (±)-1,2-diphenyl ethylene diamine, belong to organic synthesis field.
Background technology
(±)-1,2-diphenyl ethylene diamine splits preparation (1R, 2R)-(+)-1,2-diphenyl ethylene diamine and (1S, 2S)-(-)-1, the raceme of 2-diphenyl ethylene diamine chiral ligand, chirality (±)-1,2-diphenyl ethylene diamine is with a wide range of applications in chiral drug, Chiral pesticide, chiral liquid crystal, chirality spices etc.
Document 1 (Chinese Journal of Pharmaceuticals, 1993,24 (6): 2802281) reports the synthesis of one (±)-1,2-diphenyl ethylene diamine and the improvement of fractionation.Present method adopts phenyl aldehyde and liquefied ammonia to react through cyclisation; reset; obtain 2; 4; 5-triphenylimidazolyl quinoline; product is hydrolyzed to obtain again through acetylize; in described method, as acetylate: (±)-N-acetyl-N '-benzoyl-1,2-phenylethylenediamine; this product is owing to adopting glacial acetic acid and 48% Hydrogen bromide as hydrolysis medium more than 140 DEG C under reflux state; hydrolysis reaction needs 24 hours, and reaction process is serious to equipment corrosion, and product output glacial acetic acid per ton and hydrobromic mixed strong acids sewage reach more than 16 tons; and being difficult to process, environmental pollution is large.
The method that document 2 (Org.Synth., 1993,71:22 ~ 29) is reported adopts dibenzoyl and pimelinketone to synthesize through three steps, but wherein need in-78 DEG C, carry out the reduction of lithium ammonia, and operational condition is dangerous harsh.
Document 3 (Can.J.Research.1934,11:628 ~ 636.); The method that document 4 (IndianJ.Chem., 1980,19B:73.) is reported all uses sodium Metal 99.5 to reduce, and there is high potential safety hazard, industrialization difficulty.
Summary of the invention
The object of the present invention is to provide the preparation method of one (±)-1,2-diphenyl ethylene diamine.
The technical solution realizing the object of the invention is:
The preparation method of one (±)-1,2-diphenyl ethylene diamine, adopts 1,2-diphenylthanedione dioxime, with hydrazine hydrate, formic acid, sodium formiate, ammonium formiate, the one in ammonium formiate-triethylamine system is hydrogen source, at 20 DEG C-100 DEG C, employing Raney's nickel is catalyzer, gac is promotor, and in polar solvent, catalytic reduction obtains (±)-1,2-diphenyl ethylene diamine.
Wherein, the mol ratio of 1,2-diphenylthanedione dioxime and hydrazine hydrate is 1:3.0 ~ 1:10.0, preferred 1:4.6.
The mol ratio of 1,2-diphenylthanedione dioxime and formic acid is 1:4.2 ~ 1:10, preferred 1:5.2.
The mol ratio of 1,2-diphenylthanedione dioxime and sodium formiate is 1:4.2.1 ~ 1:11, preferred 1:5.0.
The mol ratio of 1,2-diphenylthanedione dioxime and ammonium formiate is 1:4.2 ~ 1:12, preferred 1:5.0.
The mol ratio of 1,2-diphenylthanedione dioxime and formic acid and triethylamine is 1:4.2:1.78 ~ 1:20:4, preferred 1:5.0:2.0.
The consumption of catalyzer is the 1-10wt% of 1,2-diphenylthanedione dioxime quality, preferred 1wt%.
Promotor gac selects 80 ~ 220 orders, preferably 120 orders; The consumption of promotor gac is 1 ~ 12wt% of 1,2-diphenylthanedione dioxime quality, preferred 3wt%
Methyl alcohol selected by polar solvent, ethanol, n-propyl alcohol, Virahol, butanols, the trimethyl carbinol, the one in methylene dichloride and 1,2-ethylene dichloride, particular methanol.Temperature of reaction preferably 60 ~ 70 DEG C.
Compared with prior art, its remarkable advantage is in the present invention:
(1) with the reductive agent Raney's nickel, cobalt chloride, iron protochloride etc. of cheapness for hydrogen source, instead of reductive agent inflammable and explosive in the production of industrialization reduction reaction as palladium/charcoal, sodium Metal 99.5 etc., solve general hydro-reduction technique and adopt hydrogen, high pressure, reductive agent exist danger and the problem of expensive catalyst; There is not burning in the reductive agent series that the present invention relates to, the possibility of blast.
(2) production unit does not need high pressure reactor, technological process environmental friendliness, and operate simple and easy, by product is few, and raw material is inexpensive, technological process safety and environmental protection, suitable easy industrial sector working condition.
(3) product yield utilizing present method to prepare is up to 86%-98%, and product purity is greater than 99%.
Embodiment
The preparation method of one (±)-1,2-diphenyl ethylene diamine, adopts 1,2-diphenylthanedione dioxime, with hydrazine hydrate, formic acid, sodium formiate, ammonium formiate, the one in ammonium formiate-triethylamine system is hydrogen source, at 20 DEG C-100 DEG C, employing Raney's nickel is catalyzer, gac is promotor, and in polar solvent, catalytic reduction obtains (±)-1,2-diphenyl ethylene diamine.
Wherein, the mol ratio of 1,2-diphenylthanedione dioxime and hydrazine hydrate is 1:3.0 ~ 1:10.0, preferred 1:4.6.
The mol ratio of 1,2-diphenylthanedione dioxime and formic acid is 1:4.2 ~ 1:10, preferred 1:5.2.
The mol ratio of 1,2-diphenylthanedione dioxime and sodium formiate is 1:4.2.1 ~ 1:11, preferred 1:5.0.
The mol ratio of 1,2-diphenylthanedione dioxime and ammonium formiate is 1:4.2 ~ 1:12, preferred 1:5.0.
The mol ratio of 1,2-diphenylthanedione dioxime and formic acid and triethylamine is 1:4.2:1.78 ~ 1:20:4, preferred 1:5.0:2.0.
The consumption of catalyzer is the 1-10wt% of 1,2-diphenylthanedione dioxime quality, preferred 1wt%.
Promotor gac selects 80 ~ 220 orders, preferably 120 orders; The consumption of promotor gac is 1 ~ 12wt% of 1,2-diphenylthanedione dioxime quality, preferred 3wt%
Methyl alcohol selected by polar solvent, ethanol, n-propyl alcohol, Virahol, butanols, the trimethyl carbinol, the one in methylene dichloride and 1,2-ethylene dichloride, particular methanol.Temperature of reaction preferably 60 ~ 70 DEG C.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
1 is added in the 500ml four-hole boiling flask that condenser is housed, 2-diphenylthanedione dioxime (48g, 0.20mol) with 260ml methyl alcohol, stirring makes it all dissolve, add 2g gac (120 order) again, 0.5g Raney's nickel, be warmed up to 60 DEG C, slowly drip the hydrazine hydrate (28.75g of 80%, 0.46mol), keep temperature of reaction between 58 DEG C-62 DEG C, reaction process has nitrogen to release, rate of addition controls at nitrogen emitting rate not easily too soon as well, liquid chromatography tracking reaction process, when raw material 1, 2-diphenylthanedione dioxime terminates reaction after disappearing, cooling mixed liquid, filter Raney's nickel and gac, cover with a small amount of water and preserve in order to applying mechanically, filtrate Distillation recovery methyl alcohol, residuum adds the heating of 200ml sherwood oil makes it all dissolve, cool and within 24 hours, filter to obtain product (±)-1, 2-diphenyl ethylene diamine 41.55g, yield 98%, chemical purity 99.57%.
Equation is as follows:
Embodiment 2
1 is added in the 500ml four-hole boiling flask that condenser is housed, 2-diphenylthanedione dioxime (48g, 0.20mol) with 300ml ethanol, stirring makes it all dissolve, add 2g gac (120 order) again, 0.5g Raney's nickel, be warmed up to 60 DEG C, slowly drip the hydrazine hydrate (28.75g of 80%, 0.46mol), keep temperature of reaction between 58 DEG C-62 DEG C, reaction process has nitrogen to release, rate of addition controls at nitrogen emitting rate not easily too soon as well, liquid chromatography tracking reaction process, when raw material 1, 2-diphenylthanedione dioxime terminates reaction after disappearing, cooling mixed liquid, filter Raney's nickel and gac, cover with a small amount of water and preserve in order to applying mechanically, filtrate Distillation recovery ethanol, residuum adds the heating of 200ml sherwood oil makes it all dissolve, cool and within 24 hours, filter to obtain product (±)-1, 2-diphenyl ethylene diamine 41.13g, yield 97%, chemical purity 99.51%.
Equation is as follows:
Embodiment 3
1 is added in the 500ml four-hole boiling flask that condenser is housed, 2-diphenylthanedione dioxime (48g, 0.20mol) with 300ml methyl alcohol, stirring makes it all dissolve, add 2g gac (120 order) again, 1.9g cobalt chloride, be warmed up to 60 DEG C, slowly drip the hydrazine hydrate (46g of 50%, 0.46mol), keep temperature of reaction between 60 DEG C-62 DEG C, reaction process has nitrogen to release, rate of addition controls at nitrogen emitting rate not easily too soon as well, liquid chromatography tracking reaction process, when raw material 1, 2-diphenylthanedione dioxime terminates reaction after disappearing, cooling mixed liquid, filter Raney's nickel and gac, cover with a small amount of water and preserve in order to applying mechanically, filtrate Distillation recovery methyl alcohol, residuum adds the heating of 200ml sherwood oil makes it all dissolve, cool and within 24 hours, filter to obtain product (±)-1, 2-diphenyl ethylene diamine 36.46g, yield 86%, chemical purity 99.1%.
Equation is as follows:
Embodiment 4
1 is added in the 500ml four-hole boiling flask that condenser is housed, 2-diphenylthanedione dioxime (48g, 0.20mol) with 240ml methyl alcohol, 60ml water stirs and makes it all dissolve, add 2g gac (120 order) again, 0.5g Raney's nickel, be warmed up to 60 DEG C, slowly drip the hydrazine hydrate (37.5g of 80%, 0.6mol), keep temperature of reaction at 62 DEG C, reaction process has nitrogen to release, rate of addition controls at nitrogen emitting rate not easily too soon as well, liquid chromatography tracking reaction process, when raw material 1, 2-diphenylthanedione dioxime terminates reaction after disappearing, cooling mixed liquid, filter Raney's nickel and gac, cover with a small amount of water and preserve in order to applying mechanically, filtrate Distillation recovery methyl alcohol, residuum adds the heating of 200ml sherwood oil makes it all dissolve, cool and within 24 hours, filter to obtain product (±)-1, 2-diphenyl ethylene diamine 40.28g, yield 95%, chemical purity 99.52%.
Equation is as follows:
Embodiment 5
1 is added in the 500ml four-hole boiling flask that condenser is housed, 2-diphenylthanedione dioxime (48g, 0.20mol) it is made all to dissolve with the stirring of 230ml ethanol, add 2g gac (120 order) again, 0.8g Raney's nickel, be warmed up to 60 DEG C, slowly drip the formic acid (56.28g of 85%, 1.04mol), keep temperature of reaction at 70 DEG C, reaction process has carbonic acid gas to release, rate of addition controls at gas emitting rate not easily too soon as well, liquid chromatography tracking reaction process, when raw material 1, 2-diphenylthanedione dioxime terminates reaction after disappearing, cooling mixed liquid, filter Raney's nickel and gac, cover with a small amount of water and preserve in order to applying mechanically, filtrate Distillation recovery ethanol, residuum adds the heating of 200ml sherwood oil makes it all dissolve, cool and within 24 hours, filter to obtain product (±)-1, 2-diphenyl ethylene diamine 38.58g, yield 91%, chemical purity 99.5%.
Equation is as follows:
Embodiment 6
1 is added in the 500ml four-hole boiling flask that condenser is housed, 2-diphenylthanedione dioxime (48g, 0.20mol) it is made all to dissolve with the stirring of 360ml methyl alcohol, add 2.5g gac (120 order) again, 0.8g Raney's nickel, be warmed up to 60 DEG C, slowly drip the ammonium formiate aqueous solution (128g of 50%, 1.0mol), keep temperature of reaction at 63 DEG C, liquid chromatography tracking reaction process, when raw material 1, 2-diphenylthanedione dioxime terminates reaction after disappearing, cooling mixed liquid, filter Raney's nickel and gac, cover with a small amount of water and preserve in order to applying mechanically, filtrate Distillation recovery methyl alcohol, residuum adds the heating of 200ml sherwood oil makes it all dissolve, cool and within 24 hours, filter to obtain product (±)-1, 2-diphenyl ethylene diamine 39.43g, yield 93%, chemical purity 99.59%.
Equation is as follows:
Embodiment 7
1 is added in the 500ml four-hole boiling flask that condenser is housed, 2-diphenylthanedione dioxime (48g, 0.20mol) it is made all to dissolve with the stirring of 360ml ethanol, add 2.5g gac (120 order) again, 0.8g Raney's nickel, be warmed up to 60 DEG C, slowly drip the aqueous sodium formate solution (227g of 30%, 1.0mol), keep temperature of reaction at 72 DEG C, liquid chromatography tracking reaction process, when raw material 1, 2-diphenylthanedione dioxime terminates reaction after disappearing, cooling mixed liquid, filter Raney's nickel and gac, washing filter cake, cover with a small amount of water and preserve in order to applying mechanically, filtrate Distillation recovery ethanol, residuum adds 120ml water and stirs precipitation solid, filter, wash to obtain filter cake, the heating of filter cake 200ml sherwood oil makes it all dissolve, cool and within 24 hours, filter to obtain product (±)-1, 2-diphenyl ethylene diamine 37.73g, yield 89%, chemical purity 99.22%.
Equation is as follows:
Embodiment 8
1 is added in the 500ml four-hole boiling flask that condenser is housed, 2-diphenylthanedione dioxime (48g, 0.20mol) with 230ml methyl alcohol, triethylamine (20.2g, 0.2mol) stirring makes it all dissolve, add 2.5g gac (120 order) again, 0.8g Raney's nickel, be warmed up to backflow, slowly drip the formic acid (54.12g of 85%, 1.0mol), keep temperature of reaction reflux state, liquid chromatography tracking reaction process, when raw material 1, 2-diphenylthanedione dioxime terminates reaction after disappearing, cooling mixed liquid, filter Raney's nickel and gac, cover with a small amount of water and preserve in order to applying mechanically, filtrate distillating recovering solvent, residuum adds the heating of 200ml sherwood oil makes it all dissolve, cool and within 24 hours, filter to obtain product (±)-1, 2-diphenyl ethylene diamine 40.7g, yield 96%, chemical purity 99.65%.
Equation is as follows:
Embodiment 9
1 is added in the 500ml four-hole boiling flask that condenser is housed, 2-diphenylthanedione dioxime (48g, 0.20mol) with 300ml methylene dichloride, triethylamine (20.2g, 0.2mol) stirring makes it all dissolve, add 2.5g gac (120 order) again, 0.8g Raney's nickel, be warmed up to backflow, slowly drip the formic acid (48.9g of 94%, 1.0mol), keep temperature of reaction reflux state, liquid chromatography tracking reaction process, when raw material 1, 2-diphenylthanedione dioxime terminates reaction after disappearing, cooling mixed liquid, filter Raney's nickel and gac, cover with a small amount of water and preserve in order to applying mechanically, filtrate Distillation recovery methylene dichloride, residuum adds the heating of 200ml sherwood oil makes it all dissolve, cool and within 24 hours, filter to obtain product (±)-1, 2-diphenyl ethylene diamine 38.58g, yield 91%, chemical purity 99.61%.
Equation is as follows:
Claims (10)
1. one kind (±)-1,2-preparation method of diphenyl ethylene diamine, is characterized in that: adopt 1,2-diphenylthanedione dioxime is raw material, with hydrazine hydrate, and formic acid, sodium formiate, ammonium formiate, the one in ammonium formiate-triethylamine system is hydrogen source, at 20 DEG C-100 DEG C, the one in Raney's nickel, cobalt chloride, iron protochloride is adopted to be catalyzer, gac is promotor, and in polar solvent, catalytic reduction obtains (±)-1,2-diphenyl ethylene diamine.
2. (±)-1,2-preparation method of diphenyl ethylene diamine according to claim 1, is characterized in that: the mol ratio of 1,2-diphenylthanedione dioxime and hydrazine hydrate is 1:3.0 ~ 1:10.0.
3. (±)-1,2-preparation method of diphenyl ethylene diamine according to claim 1, is characterized in that: the mol ratio of 1,2-diphenylthanedione dioxime and formic acid is 1:4.2 ~ 1:10.
4. (±)-1,2-preparation method of diphenyl ethylene diamine according to claim 1, is characterized in that: the mol ratio of 1,2-diphenylthanedione dioxime and sodium formiate is 1:4.2.1 ~ 1:11.
5. (±)-1,2-preparation method of diphenyl ethylene diamine according to claim 1, is characterized in that: the mol ratio of 1,2-diphenylthanedione dioxime and ammonium formiate is 1:4.2 ~ 1:12.
6. (±)-1,2-preparation method of diphenyl ethylene diamine according to claim 1, is characterized in that: the mol ratio of 1,2-diphenylthanedione dioxime and formic acid and triethylamine is 1:4.2:1.78 ~ 1:20:4.
7. (±)-1,2-preparation method of diphenyl ethylene diamine according to claim 1, is characterized in that: the consumption of catalyzer is the 1-10wt% of 1,2-diphenylthanedione dioxime quality.
8. (±)-1,2-preparation method of diphenyl ethylene diamine according to claim 1, it is characterized in that: promotor gac selects 80 ~ 220 orders, the consumption of promotor gac is 1 ~ 12wt% of 1,2-diphenylthanedione dioxime quality.
9. (±)-1,2-preparation method of diphenyl ethylene diamine according to claim 1, is characterized in that: methyl alcohol selected by polar solvent, ethanol, n-propyl alcohol, Virahol, butanols, the trimethyl carbinol, the one in methylene dichloride and 1,2-ethylene dichloride.
10. (±)-1,2-preparation method of diphenyl ethylene diamine according to claim 1, is characterized in that: temperature of reaction is 60 ~ 70 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920654A (en) * | 2022-04-27 | 2022-08-19 | 宁波赜军医药科技有限公司 | Method for preparing (+/-) -1, 2-diphenylethylenediamine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2746959A (en) * | 1953-06-02 | 1956-05-22 | American Home Prod | Diphenylethylenediamine-penicillin salt |
| CN101417952A (en) * | 2008-12-01 | 2009-04-29 | 宁波万华聚氨酯有限公司 | A preparation method of 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine |
| CN101735080A (en) * | 2009-12-18 | 2010-06-16 | 重庆浩康医药化工有限公司 | Process for synthesizing trans-4-amino-1-adamantanol hydrochloride |
| CN103249711A (en) * | 2010-12-03 | 2013-08-14 | 宝洁公司 | Process for preparation of 2-ethoxymethyl-1,4-benzenediamine, its derivatives thereof and the salts thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2746959A (en) * | 1953-06-02 | 1956-05-22 | American Home Prod | Diphenylethylenediamine-penicillin salt |
| CN101417952A (en) * | 2008-12-01 | 2009-04-29 | 宁波万华聚氨酯有限公司 | A preparation method of 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine |
| CN101735080A (en) * | 2009-12-18 | 2010-06-16 | 重庆浩康医药化工有限公司 | Process for synthesizing trans-4-amino-1-adamantanol hydrochloride |
| CN103249711A (en) * | 2010-12-03 | 2013-08-14 | 宝洁公司 | Process for preparation of 2-ethoxymethyl-1,4-benzenediamine, its derivatives thereof and the salts thereof |
Non-Patent Citations (1)
| Title |
|---|
| MURAKAMI, MASUO等: "Homogeneous hydrogenation. VI. Stereospecificity of homogeneous hydrogenation with cyanocobalt or chloropentamminecobalt complex", 《NIPPON KAGAKU ZASSHI》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920654A (en) * | 2022-04-27 | 2022-08-19 | 宁波赜军医药科技有限公司 | Method for preparing (+/-) -1, 2-diphenylethylenediamine |
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