CN117486730A - Preparation method of dicyclohexyl methylamine - Google Patents
Preparation method of dicyclohexyl methylamine Download PDFInfo
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- CN117486730A CN117486730A CN202311360373.5A CN202311360373A CN117486730A CN 117486730 A CN117486730 A CN 117486730A CN 202311360373 A CN202311360373 A CN 202311360373A CN 117486730 A CN117486730 A CN 117486730A
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- hydrazine hydrate
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- QVQGTNFYPJQJNM-UHFFFAOYSA-N dicyclohexylmethanamine Chemical compound C1CCCCC1C(N)C1CCCCC1 QVQGTNFYPJQJNM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 16
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229940126062 Compound A Drugs 0.000 claims abstract description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000012965 benzophenone Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- KAVKNHPXAMTURG-UHFFFAOYSA-N n-(4-bromonaphthalen-1-yl)acetamide Chemical compound C1=CC=C2C(NC(=O)C)=CC=C(Br)C2=C1 KAVKNHPXAMTURG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000002829 reductive effect Effects 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWXWPPKDQOWNSX-UHFFFAOYSA-N dicyclohexylmethanone Chemical compound C1CCCCC1C(=O)C1CCCCC1 TWXWPPKDQOWNSX-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CFLVLIPWELANNE-UHFFFAOYSA-N 1,2-dibenzhydrylhydrazine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)NNC(C=1C=CC=CC=1)C1=CC=CC=C1 CFLVLIPWELANNE-UHFFFAOYSA-N 0.000 description 2
- GXNVARTZYHDDNN-UHFFFAOYSA-N 1,2-dibenzylhydrazine Chemical compound C=1C=CC=CC=1CNNCC1=CC=CC=C1 GXNVARTZYHDDNN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- -1 amine compound Chemical class 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JVDQYSIJBRTRMS-UHFFFAOYSA-N 3-bromo-2-chloro-6-methylpyridine Chemical compound CC1=CC=C(Br)C(Cl)=N1 JVDQYSIJBRTRMS-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/42—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitrogen-to-nitrogen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/16—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings other than six-membered aromatic rings
- C07C211/17—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings other than six-membered aromatic rings containing only non-condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C243/10—Hydrazines
- C07C243/22—Hydrazines having nitrogen atoms of hydrazine groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of dicyclohexyl methylamine, which comprises the following steps: mixing diphenyl ketone and hydrazine hydrate, and synthesizing a compound A under the catalysis of protonic acid; reducing the compound A to obtain a compound B; and finally, carrying out catalytic hydrogenation on the compound B to obtain a target product dicyclohexylmethylamine. The method has the advantages of mild reaction conditions, abundant raw material sources, simple operation, high raw material conversion rate, few byproducts and high purity, and can be applied to industrial production.
Description
Technical Field
The invention relates to a preparation method of dicyclohexylmethylamine, belonging to the technical field of organic chemical synthesis.
Background
Dicyclohexylmethylamine, english name: dicyclohexylmethanamine. Dicyclohexylmethylamine is an organic amine compound and is widely used in a plurality of fields such as medical intermediates, pesticide intermediates and the like, surfactants, additives and the like. Dicyclohexylmethylamine is used as a nitrogen base with large volume, and is often used for salifying with carboxylic acid to further perform purification because of fat solubility and water solubility, for example, amino acid compounds are salified with dicyclohexylmethylamine, so that a crystal form which is easy to filter can be obtained; and because of the structure, the catalyst can be used as a base for the coupling reaction, so that the coupling reaction is more stable.
There are two synthetic methods reported so far for dicyclohexylmethylamine, one is reductive amination of dicyclohexylketone with ammonia, as in document [ Organic Letters,2008, vol.10, #23, p.5429-5432] or document [ Journal of the Chemical society. Perkin transformations I,1997, #17, p.2607-2616], and the other is a reaction using dicyclohexylketone to form a ketoxime with hydroxylamine followed by reduction, as in documents [ Journal of Organic Chemistry,1969, vol.34, #6, p.1817-1821]. Both methods use dicyclohexyl ketone as raw material, and the dicyclohexyl ketone has high selling price and is not easy to purchase in a large amount. The product of the first method is not easy to purify, flammable metal is needed to be used as a catalyst for reduction in the second method, and the reaction condition is high, so that the method is not suitable for large-scale production.
Aiming at the defects of poor safety, expensive raw materials and the like of the traditional synthesis method, the invention provides a brand-new synthesis route of dicyclohexylmethylamine, which has the characteristics of low raw material price, easy purchase, high yield, high product purity and the like, thereby meeting the increasing market demands.
Disclosure of Invention
In order to overcome the technical defects, the invention provides a preparation method of dicyclohexylmethylamine, which is characterized in that diphenyl ketone and hydrazine hydrate are mixed and then a compound A is synthesized under the catalysis of protonic acid; reducing the compound A to obtain a compound B (N, N' -bis (benzhydryl) hydrazine); and finally, carrying out catalytic hydrogenation on the compound B to obtain a target product compound C (dicyclohexylmethylamine). The method has the advantages of mild reaction conditions, rich raw material sources, simple operation, high raw material conversion rate, few byproducts and convenient purification, and can be applied to industrial production.
The preparation method of the 2-chloro-3-bromo-6-methylpyridine, disclosed by the invention, is carried out by adopting three steps of reactions, and comprises the following steps:
the first step: mixing benzophenone, hydrazine hydrate, protonic acid, a catalyst and an alcohol solvent, heating and condensing to obtain a compound A; the reaction equation is expressed as follows:
and a second step of: mixing the compound A with a mixed solvent, and adding a reducing reagent for reduction to obtain a compound B; the reaction equation is expressed as follows:
and a third step of: the compound B, palladium carbon and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate are catalytically hydrogenated at 30-45Psi to obtain the compound C. The reaction equation is expressed as follows:
further, in the above technical scheme, in the first step, the hydrazine hydrate is selected from 40% hydrazine hydrate or 85% hydrazine hydrate, preferably 85% hydrazine hydrate.
Further, in the above technical scheme, after 85% hydrazine hydrate is preferred in the first step, the molar ratio of the benzophenone, hydrazine hydrate, protonic acid and catalyst is 2.0:5.0:0.1:0.03.
further, in the above technical scheme, in the second step, the mixed solvent is selected from a mixed solvent of methanol or ethanol and dichloromethane.
Further, in the above technical scheme, in the second step, the reducing agent is selected from sodium borohydride or sodium borohydride acetate, respectively.
Further, in the above technical scheme, in the second step, the molar ratio of the compound a to the reducing agent is 1:2.25-2.75.
Further, in the above technical scheme, in the third step, the molar ratio of the compound B to sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate is 1:0.05-0.10.
Compared with the prior art, the invention has the beneficial effects that: the raw materials are easy to purchase, the conversion rate is high, the byproducts are few, the purity of the product after common distillation is up to 99.7%, and the method is suitable for industrial scale production.
Drawings
FIG. 1 shows the HNMR spectrum of dicyclohexylmethylamine product obtained in example 5.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following are specific embodiments of the invention; these examples may further supplement and illustrate the present invention; the present invention is not limited to these examples.
Example 1
In a reaction kettle containing a reflux device, 127.6g (0.7 mol) of benzophenone, 22.4g (0.13 mol) of p-toluenesulfonic acid, 10.7g (0.021 mol) of tris (pentafluorophenyl) boron and 1200mL of ethanol are mixed, the temperature is raised to 40 ℃, 224.4g (7 mol) of 40% hydrazine hydrate is dropwise added, then reflux is carried out for 10 hours, a reduced pressure distillation device is changed, the temperature is reduced to 40-45 ℃, vacuum pumping is carried out, reduced pressure distillation is carried out until the residual volume is 3, 1200mL of toluene is added, reduced pressure distillation is continued until the residual volume is 3, 1200mL of toluene and 127.6g (0.7 mol) of benzophenone are added, the temperature is raised to reflux reaction for 8 hours, reduced pressure distillation is carried out until the residual volume is 3.5, 800mL of ethanol is added, the temperature is reduced to 15-20 ℃, a large amount of white solid is separated out, the filtration is carried out, a filter cake is leached by ethanol, and the drying is carried out to obtain 225.4g (0.626 mol) of benzophenone with the nitrogen, and the yield is 89.4%. 1 HNMR(400MHz,CDCl3):7.53-7.49(m,4H),7.47-7.27(m,16H).
Example 2
In a reaction kettle containing a reflux device, 127.6g (0.7 mol) of benzophenone, 12.1g (0.07 mol) of p-toluenesulfonic acid, 10.7g (0.021 mol) of tris (pentafluorophenyl) boron and 1400mL of methanol are mixed, the temperature is raised to 40 ℃, 132g (3.5 mol) of 85% hydrazine hydrate is dropwise added, then reflux is carried out for 6 hours, a reduced pressure distillation device is changed, the temperature is reduced to 40-45 ℃, vacuum pumping is carried out, reduced pressure distillation is carried out until the residual volume is 3, 1200mL of toluene is added, reduced pressure distillation is continued until the residual volume is 3, 1200mL of toluene and 127.6g (0.7 mol) of benzophenone are added, the temperature is raised to reflux reaction for 8 hours, reduced pressure distillation is carried out until the residual volume is 3.5, 1000mL of methanol is added, the temperature is reduced to 15-20 ℃, a large amount of white solid is separated out, filtration, a filter cake is leached by methanol, and drying is carried out to obtain 230.3g (0.639 mol) of benzophenone with nitrogen, and the yield is 91.3%.
Example 3
Under the protection of nitrogen, 144.2g (0.4 mol) of benzophenone with nitrogen, 100mL of methanol and 600mL of methylene dichloride are mixed, cooled to 0-5 ℃, 211.9g (1.0 mol) of sodium borohydride acetate is added for 10 times, the temperature is raised to room temperature for reaction for 3 hours, the reduced pressure concentration is carried out to a non-flowing liquid, 0.5N hydrochloric acid is added to adjust the pH value to 8-8.5, the mixture is stood for layering, the water phase is extracted by 200mL of methylene dichloride, the organic phases are combined and washed, the solvent is distilled off by the reduced pressure of the organic phase, 600mL of methanol is added, the temperature is reduced to 0 ℃, a large amount of white solid is separated out, the mixture is filtered and dried to obtain 134.7g (0.3696 mol) of N, N' -bis-benzyl hydrazine, the yield is 92.4%, and the HPLC is 99.1%. 1 HNMR(400MHz,CDCl3):7.80-7.76(m,4H),7.59-7.31(m,16H),5.12-4.89(m,2H),4.08(t,2H).
Example 4
Under the condition of blowing nitrogen, 144.2g (0.4 mol) of benzophenone with nitrogen, 100mL of methanol and 600mL of methylene dichloride are mixed, the temperature is reduced to 0-5 ℃, 33.3g (0.88 mol) of sodium borohydride is added for 10 times, the temperature is raised to room temperature for reaction for 3 hours, the reduced pressure concentration is carried out until no fluid is carried out, 0.5N hydrochloric acid is added for regulating pH=8-8.5, standing and layering are carried out, the organic phase is washed by water, the solvent is distilled off under reduced pressure, 600mL of methanol is added, the temperature is reduced to 0 ℃, a large amount of white solid is separated out, the filtration and the drying are carried out, and the N, N' -bisbenzylhydrazine 127.1 (0.3488 mol) is obtained, the yield is 87.2%, and the HPLC is 99.4%. Yield 90.4%, HPLC 99.7%.
Example 5
In a high-pressure stainless steel reaction, 109.3g (0.3 mol) of N, N' -bis (benzhydryl) hydrazine, 26.6g (0.03 mol) of 10% Pd/C5 g of sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, 1000mL of ethanol, 5mL of acetic acid and 3 times of nitrogen substitution, pressurizing to 20-25Psi after 3 times of hydrogen substitution, heating to 50-55 ℃, continuing pressurizing to 30-45Psi, reacting for 12 hours at the temperature and the pressure, TLC detecting the reaction condition, cooling to room temperature, filtering, eluting a filter cake by ethanol, putting the filter cake into a rotary evaporator, steaming until dry, finally obtaining a crude product, and collecting 94.6g (0.484 mol) of dicyclohexylmethylamine with the main fraction at 100-120 ℃ by reduced pressure distillation, wherein the yield is 80.7%, and GC 99.8%. 1 HNMR(400MHz,CDCl3):2.19(t,1H),1.78-1.57(m,10H),1.39-1.05(m,14H).
In the foregoing, various modifications or additions and substitutions can be made by those skilled in the art to the described embodiments without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (7)
1. A process for the preparation of dicyclohexylmethylamine, comprising the steps of:
the first step: mixing benzophenone, hydrazine hydrate, protonic acid, a catalyst and an alcohol solvent, heating and condensing to obtain a compound A;
and a second step of: mixing the compound A with a mixed solvent, and adding a reducing reagent for reduction to obtain a compound B;
and a third step of: the compound B, palladium carbon and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate are catalytically hydrogenated at 30-45Psi to obtain the compound C.
2. The method for preparing dicyclohexylmethylamine as claimed in claim 1, wherein: in the first step, the hydrazine hydrate is selected from 40% hydrazine hydrate or 85% hydrazine hydrate.
3. The method for preparing dicyclohexylmethylamine as claimed in claim 1, wherein: in the first step, the protic acid, catalyst and alcohol solvent are selected from p-toluene sulfonic acid, tris (pentafluorophenyl) boron and methanol or ethanol, respectively.
4. The method for preparing dicyclohexylmethylamine as claimed in claim 1, wherein: in the first step, the molar ratio of the diphenyl ketone, the hydrazine hydrate, the protonic acid and the catalyst is 2.0:5.0-10.0:0.1-0.3:0.03.
5. the method for preparing dicyclohexylmethylamine as claimed in claim 1, wherein:
in the second step, the mixed solvent and the reducing agent are respectively selected from mixed solvents of methanol or ethanol and dichloromethane, sodium borohydride or sodium borohydride acetate.
6. The method for preparing dicyclohexylmethylamine as claimed in claim 1, wherein:
in the second step, the molar ratio of the compound A to the reducing agent is 1:2.25-2.75.
7. The method for preparing dicyclohexylmethylamine as claimed in claim 1, wherein:
in the third step, the molar ratio of the compound B to sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate is 1:0.05-0.10.
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2023
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