CN114105780A - Synthesis method of isooctylamine and derivatives by one-pot method - Google Patents
Synthesis method of isooctylamine and derivatives by one-pot method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 28
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 10
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 58
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000000498 cooling water Substances 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 7
- -1 isooctyl imino succinic acid monosodium salt Chemical compound 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 238000006268 reductive amination reaction Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000005882 aldol condensation reaction Methods 0.000 description 4
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 150000002081 enamines Chemical class 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005932 reductive alkylation reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LCTORNIWLGOBPB-GASJEMHNSA-N (3r,4s,5s,6r)-2-amino-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound NC1(O)O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O LCTORNIWLGOBPB-GASJEMHNSA-N 0.000 description 1
- PYLMCYQHBRSDND-VURMDHGXSA-N (Z)-2-ethyl-2-hexenal Chemical compound CCC\C=C(\CC)C=O PYLMCYQHBRSDND-VURMDHGXSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910004721 HSiCl3 Inorganic materials 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- LUIGSJYSMIUMPK-UHFFFAOYSA-N propane-1-sulfonoperoxoic acid Chemical compound CCCS(=O)(=O)OO LUIGSJYSMIUMPK-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The synthesis method of isooctylamine and derivatives by a one-pot method is technically characterized by comprising the following steps of: step 1, adding n-butyl aldehyde, skeletal nickel or skeletal copper or a mixture thereof and pure water washing liquor into a high-pressure reaction kettle, and stirring the reaction kettle at a constant speed of 500r/h under the nitrogen atmosphere of 0.2 MPa; step 2, reacting at the temperature of less than or equal to 25 ℃ for 1 hour under normal pressure, slowly heating to 35 ℃, reacting for 0.5 hour, and quickly cooling to the temperature below 35 ℃ in a cooling water environment; step 3, introducing liquid ammonia or dimethylamine, injecting hydrogen, boosting (and maintaining) the pressure to 3.0MPa, increasing the stirring speed to 700 r/h, and finishing after no hydrogen is absorbed any more; and 4, rectifying and collecting fractions at 155-156 ℃. The method has the advantages of simple process, easy small-scale mass production and the like.
Description
Technical Field
The invention relates to a synthetic method of organic amines, in particular to an amination reduction reaction of unsaturated aldehyde substances, and specifically relates to a synthetic method of isooctylamine and derivatives by a one-pot method.
Background
Isooctylamine is an excellent fine chemical raw material and is widely used in the fields of surfactants, fine chemical intermediates, dye raw materials and pharmaceutical intermediates. For example, isooctyl imino succinic acid monosodium salt is prepared by Michael addition of isooctyl amine and succinic acid, N-carboxyethyl isooctyl amino propionic acid sodium is prepared by addition of the isooctyl imino succinic acid monosodium salt and acrylic acid, the N, N-dihydroxyethyl isooctyl amine is prepared by reaction of the N, N-dihydroxyethyl isooctyl amine and ethylene oxide, and the low-foam amphoteric surfactant is obtained by reaction of the N, N-dimethyl octylamine and 3-chloro-2-sodium hydroxy propanesulfonate, and is one of the known amphoteric surfactants with lower surface tension and excellent performance.
Direct Reductive Amination (DRA) is the most practical method for synthesizing chiral amine drugs at present, and can construct a C-N bond in one step. AH (Asymmetric Hydrogenation) and DRA can share clean reducing agent H2And the byproduct is only H2O, which is a green, economical and efficient method for synthesizing the chiral amine compound. Yuan-Shuai of northwest agriculture and forestry science and technology university discloses that AH with C = C bond and DRA with C = O bond in alpha, beta-unsaturated aldehyde are realized by one-pot method under catalysis of Rh- (R) -Segphos in the synthesis of chiral secondary amine and antifungal activity thereof by an asymmetric hydrogenation and direct reductive amination serial connection method, and a series of chiral secondary amines are successfully synthesized. In addition, the abstract lists the specific process parameters of the N,2, 3-triphenylpropylamine, wherein the hydrogen pressure is 50atm, the reaction temperature is 60 ℃, and the reaction time is 24 h.
Since the above studies are aimed at screening chiral compounds, which have higher requirements for the use of catalysts, detailed description is given in table 2-2 of table 19 of the paper, in which metallic Ir is less expensive but not given enantiomeric excess value and is abandoned, and metallic Rh is used without exception in 8 other catalyst combinations, but the current commercial metallic Rh price fluctuates above 3000/g (gold screening data). Therefore, if the problem of catalyst loss is considered, the process flow can be difficult to recover the cost, so that the process flow has no industrial prospect.
1.3.2 of the research background of this paper also mentions other aldehyde reductive amination reactions, e.g. 2% manganese as catalyst, with hydrogen and imine intermediates; chiral phosphoric acid is used as a catalyst, hans ester is used as a hydrogen source, and the chiral phosphoric acid reacts with aniline and an aniline derivative; with chiral Lewis base catalysts, with HSiCl3As a source of hydrogen, with an aniline derivative.
Chenina et al, in "research progress on a reaction catalyst for synthesizing octenal by self-condensation of n-butyl aldehyde", chemical reports (2013), 76 (4) disclose that water is used as a solvent, and polyvinylpyrrolidone or a solid organic base (e.g., basic resins having a tertiary amine as an end group) or the like is used as a catalyst under normal pressure to catalyze n-butyl aldehyde to perform aldol condensation reaction to produce octenal (2-ethyl-2-hexenal) with 0.5% of liquid inorganic base (NaOH), solid inorganic base (e.g., metal oxides, hydrotalcites) or the like, and do not disclose application of nickel or copper as a catalyst to catalyze the condensation reaction.
Regarding the skeletal metals, Zhou Xiao Jian et al, the influence of substituents on the benzene ring and alkylating alcohols on the synthesis of N-alkylarylamines by reductive alkylation, proceedings of university of general Physics (1999), 39 (1), discloses the preparation of N-alkylarylamines by reductive alkylation of aromatic nitro compounds with skeletal nickel selective catalysis.
Regarding reductive amination reaction using nickel catalysis, Qijiahui and the like, in the reductive amination reaction of glucose using activated carbon-supported nano nickel catalysis, chemical engineering progress (2011), 30 (6), it is disclosed that nano nickel (Ni/AC) supported by activated carbon is used as a catalyst to catalytically prepare the glucoseamine crystal in a hydrogen environment of 2.5MPa or 5.0 MPa. The particle size of the nano nickel is about 20nm to 30 nm.
Regarding the performance difference between the nano nickel and the skeletal nickel, the detailed comparison between the catalytic performances of the nano nickel and the skeletal nickel in journal and the detailed comparison between the nano nickel and the skeletal nickel in the chemical industry bulletin (2003), 54 (5) show that the skeletal nickel is a typical hydrogenation catalyst in the hydrogenation reaction of nitrophenol, and the skeletal nickel catalyst has the advantages of low price and the like, but researches show that the catalytic selectivity of the skeletal nickel is low. And also relatively easy to inactivate. Within the same reaction time, the yield of the nano nickel is the skeletal nickelThe yield is more than 2 times. The specific surface areas of the fresh nano nickel and the fresh skeleton nickel are 43.58m respectively2 ·g-1，71.18 m2 ·g-1And after the nickel is recycled, the nano nickel is subjected to agglomeration, the particle size is increased, and the change of the skeleton nickel is small.
In addition, in the prior art, organic amines can also be prepared by dehydration of alcohols with ammonia at elevated temperatures and pressures. The invention patent with the publication number of CN1250517C discloses a method for synthesizing isooctylamine, which takes isooctanol as a raw material and Cu-Co/Al2O3Mixing isooctyl alcohol, ammonia gas and hydrogen gas under the conditions of 0.1-2.0 Mpa and 150-280 ℃ by using diatomite as a catalyst to react, and finally obtaining about 66wt% of 2-ethylhexyl amine (final product), about 30wt% of 2-ethylhexanol and about 3.0wt% of by-products. The technical proposal also discloses a preparation method of the used catalyst, and does not disclose whether other similar catalysts can be used.
Disclosure of Invention
The invention aims to provide a synthetic method of isooctylamine and derivatives by one-pot method, which fundamentally solves the problems and has the advantages of simple process, easy small-scale mass production and the like. The raw material n-butyraldehyde is subjected to condensation reaction under the catalysis of alkaline skeletal nickel to obtain octenal, and the final product isooctylamine is obtained through ammoniation and hydrogenation of the octenal, so that the reaction condition requirement is lower.
In order to achieve the purpose, the invention provides the following technical scheme: the synthesis method of isooctylamine and derivatives by one-pot boiling comprises the following steps:
step 1, adding 100 parts by weight of n-butyl aldehyde, 4-6 parts by weight of alkaline skeleton nickel or skeleton copper or a mixture thereof into a 500ml high-pressure reaction kettle, performing nitrogen replacement for three times at 0.2MPa, and stirring the reaction kettle at a constant speed of 500r/h in a nitrogen atmosphere; the weight ratio of the framework metal to the n-butyraldehyde is 1: 10-1: 100, respectively;
step 2, reacting at the temperature of less than or equal to 25 ℃ for 1 hour under normal pressure, slowly heating to 35 ℃, reacting for 0.5 hour, slowly heating to 60 ℃ for reacting for 0.5 hour, slowly heating to 90 ℃ for reacting for 0.5 hour, and rapidly cooling to below 35 ℃ in a cooling water environment;
and 3, replacing three times with 0.2MPa hydrogen, introducing liquid ammonia or dimethylamine, wherein the feeding molar ratio of the liquid ammonia or dimethylamine to the n-butyl aldehyde is more than or equal to 0.55: 1, filling hydrogen, increasing the pressure to 3.0MPa (and keeping the pressure), increasing the stirring speed to 700 r/h, heating to 90 ℃ to activate the reaction, and keeping the reaction for 0.5h after no hydrogen is absorbed;
and 4, filtering the mother liquor, recovering the catalyst, distilling off ammonia gas at normal pressure, and rectifying and collecting fractions at 155-156 ℃.
By converting the-C = O bond to the-C-N bond through step 3, two sets of reactions may be involved in the mixed system:
in the above reaction formula, R1Predominantly ethyl, R2Mainly a methyl group, and the like,R3mainly hydrogen.
The invention has the beneficial effects that:
the whole synthesis process is mainly divided into two stages: in the first stage, n-butyraldehyde serving as a raw material is selected, alkaline framework nickel or framework copper or a mixture of the alkaline framework nickel and the framework copper is used as a catalyst, and aldol condensation reaction is carried out under the condition of gradually increasing the temperature under the protection of nitrogen. The second stage can be continued without extracting any reactant, the nitrogen protection atmosphere is replaced by high-pressure hydrogen protection atmosphere, ammoniation and hydrogenation reaction are carried out under the conditions of saturated ammonia (amine) and saturated hydrogen, and finally the product isooctylamine is obtained. The first stage reaction and the second stage reaction can share the framework metal catalyst, and the two-stage reaction can be directly carried out without additionally adding other raw materials and extracting byproducts. The reaction condition is mild, the process is simpler and safer, and the byproduct is only H2And O, the production process is more environment-friendly.
In the first stage, n-butyraldehyde is reacted in alpha position and beta position as much as possible by a method of gradually raising the temperature, so that the generation of by-products (such as polyacetals and disproportionation reaction) in a high-temperature environment is effectively reduced, n-butyraldehyde is reacted to generate octenal as much as possible, and the yield of isooctylamine in the second stage reaction is improved. In two n-butyraldehyde molecules participating in the reaction, O and H at the alpha position of one n-butyraldehyde are activated, H at the beta position of the other n-butyraldehyde is activated, and the O and H at the alpha position are combined with the H at the beta position to generate more stable product water, so that the reaction is promoted to be carried out in the forward direction, and two n-butyraldehydes are condensed to synthesize octenal. In actual production, the raw material price of octenal is far higher than that of raw material n-butyraldehyde, so the synthesis of octenal by adopting the n-butyraldehyde one-pot method is a synthesis method with higher titer.
In the second stage, the ammoniation hydrogenation of aldehyde and ketone usually is the reaction of saturated aldehyde or ketone and ammonia (or amine), and the process conditions are mild, so that the method is suitable for the production of small-scale multi-variety series products, such as the ammoniation hydrogenation of octenal and liquid ammonia to obtain octylamine, and the ammoniation hydrogenation of octenal and dimethylamine to obtain N-octyldimethylamine and the like. During the ammoniation hydrogenation of the olefine aldehyde, the double bonds of the enamine and the hydrocarbon are hydrogenated together, an imine intermediate with higher activity is more likely to be obtained in a reaction mixed system, and the imine intermediate reacts with hydrogen to generate a more stable methylamine substrate.
In summary, the main improvement points of the process of the present invention mainly include the following points: the cheap skeleton nickel or skeleton copper is selected to replace the expensive Rh- (R) -Segphos catalyst or nano nickel catalyst in the prior art, and the catalyst is used for catalyzing the condensation of n-butyl aldehyde and the hydrogenation and ammoniation of octenal on the other hand, thereby effectively reducing the production cost of isooctylamine. The copper-nickel base catalyst is more suitable for the production and application of low-value and small-scale industrial basic raw materials.
Detailed Description
The present invention will be described in detail below with reference to specific examples. The synthesis method of isooctylamine and derivatives by one-pot method mainly relates to the following reaction steps:
step 1, adding 100 parts by weight of n-butyl aldehyde, 4-6 parts by weight of alkaline skeleton nickel or skeleton copper or a mixture thereof serving as a catalyst into a high-pressure reaction kettle, performing nitrogen replacement for three times at 0.2MPa, and stirring the reaction kettle at a constant speed of 500r/h in a nitrogen atmosphere; the weight ratio of the framework metal to the n-butyraldehyde is 1: 10-1: 100, respectively;
and 2, reacting at the temperature of less than or equal to 25 ℃ for 1 hour under normal pressure, slowly heating to 35 ℃, reacting for 0.5 hour, slowly heating to 60 ℃ for reacting for 0.5 hour, slowly heating to 90 ℃ for reacting for 0.5 hour, and quickly cooling to below 35 ℃ in a cooling water environment. The following aldol condensation reaction mainly occurs during the gradual temperature rise process in this step.
Step 3, after condensation is finished, separation is not needed, 0.2MPa hydrogen is used for replacement for three times, liquid ammonia or dimethylamine is introduced, and the molar ratio of the liquid ammonia or dimethylamine to the octenal is more than or equal to 1.1: 1, namely, the liquid ammonia is excessive, hydrogen is injected into the liquid ammonia, the pressure is increased to 3.0MPa (and maintained, about 30 atm), the stirring speed is increased to 700 r/h, the temperature is increased to 90-100 ℃ to activate the reaction, the temperature is monitored in real time in the reaction process to avoid the increase of the alcohol amount over 110 ℃, the reaction is continued to be maintained for about 0.5h after the reaction is not absorbed any more, and the reaction process is terminated. This step mainly takes place following ammoniation hydrogenation reactions.
) Ammoniation reaction:
3) hydrogenation reaction:
the-C = O bond at the α -position of octenal is finally substituted by a-C-N bond by an ammoniation hydrogenation reaction.
The reactions from (2) to (v) are in the same reaction system, when the temperature is raised to 90 ℃, carbon atoms at two ends of unsaturated bonds are activated, a large amount of negative electricity-NH and positive electricity free H & lt + & gt exist in the reaction system, and oxygen atoms of end acyl groups are more easily replaced than-NH, so that the free negative electricity-NH is replaced by negative electricity-OH which is easy to fall off, and the free negative electricity-OH is rapidly combined with the free H & lt + & gt to generate water, so that the reaction from (2) to (v) is promoted to be carried out in the forward direction. Meanwhile, because the intermediate with unsaturated bonded terminal amine in the reaction II is extremely active, the unsaturated bond is immediately combined with free H + to generate hydrogenation reaction after being generated, and the intermediate only participates in the reaction III instantly, so that the resolution explanation is carried out for conveniently explaining the reaction principle.
In the third reaction step, the reaction kettle is in a high-pressure hydrogen atmosphere, namely, hydrogen is excessive, liquid ammonia with the mole number higher than that of the octenal is added, so that the forward reaction is facilitated, and when the concentration of the enamine intermediate in the reaction system is reduced, the forward reaction is facilitated until the octenal completely participates in the reaction. Therefore, it is possible to determine whether the reaction is complete by monitoring the amount of hydrogen. For example, the pressure threshold may be set in a constant pressure manner, and when the pressure in the autoclave body is lower than the threshold, the air inlet valve of the hydrogen inlet pipeline is automatically opened. When the pressure in the reaction kettle is kept constant for a long time, the reaction is complete. Therefore, in actual production, the reaction endpoint can be remotely monitored by detecting the opening/closing state interval time of the intake valve.
And 4, filtering the mother liquor, recovering the catalyst, distilling ammonia gas or dimethylamine gas at normal pressure, rectifying and collecting fractions at 155-156 ℃.
Example 1
Step 1, adding 100g of n-butyraldehyde (AR, 98 percent, Shanghai Michelin biochemical technology), 4.5g of skeletal nickel and 100 parts by weight of pure water washing liquor with pH = 7.5-8 into a 500ml high-pressure reaction kettle, performing nitrogen replacement for three times under 0.2MPa, and stirring the reaction kettle at a constant speed of 500r/h under a nitrogen atmosphere; the weight ratio of the framework metal to the n-butyraldehyde is 1: 10-1: 100, respectively;
and 2, reacting at the temperature of less than or equal to 25 ℃ for 1 hour under normal pressure, slowly heating to 35 ℃, reacting for 0.5 hour, slowly heating to 60 ℃ for reacting for 0.5 hour, slowly heating to 90 ℃ for reacting for 0.5 hour, and quickly cooling to below 35 ℃ in a cooling water environment. The following aldol condensation reaction mainly occurs in the gradual temperature rise process of the step, and the low-temperature condensation can avoid the formation of the polyacetals.
And 3, after condensation is finished, separation is not needed, 0.2MPa hydrogen is used for replacing for three times, 15g of liquid ammonia (more than or equal to 99% of Luxi chemical industry) is introduced, the hydrogen is injected and the pressure is increased to (and maintained at) 3.0MPa, the stirring speed is increased to 700 r/h, the temperature is increased to 90 ℃ to activate reaction, the reaction process is monitored in real time to avoid the temperature exceeding 110 ℃, the alcohol content is increased when the temperature is increased, and the reaction process is continued for about 0.5h after the reaction does not absorb hydrogen any more, and then the reaction process is terminated. This step mainly takes place the following reaction.
And 4, filtering the mother liquor, recovering the catalyst, distilling off ammonia gas at normal pressure, rectifying and collecting fractions at 155-156 ℃, wherein the yield is 85.3%.
Example 2
And (3) replacing the liquid ammonia in the step (3) with 40g of dimethylamine (more than or equal to 99 percent, ZiboKai commercial Co., Ltd.), and distilling off the dimethylamine gas in the step (4) to obtain the yield of 81.7 percent. Other reaction conditions were the same as in example 1.
Example 3
The skeleton nickel in the step 1 is replaced by a mixture of 3g of skeleton nickel and 1.5g of skeleton copper, different manufacturers (Zibomega Kai commercial Co., Ltd.) are selected for liquid ammonia (not less than 99%) in the step 3, and the yield is 89.2%. Other reaction conditions were the same as in example 1.
| Feed proportioning | Example 1 | Example 2 | Example 3 |
| N-butyraldehyde | 100g | 100g | 100g |
| Skeletal nickel | 4.5g | 4.5g | 3g |
| Skeleton copper | 0g | 0g | 1.5g |
| Dimethylamine | 0g | 40g | 0g |
| Liquid nitrogen | 15g | 0g | 15g |
| Yield of | 85.3% | 81.7% | 89.2% |
Claims (2)
1. The method for synthesizing isooctylamine and derivatives by one-pot boiling is characterized by comprising the following steps of:
step 1, adding 100 parts by weight of n-butyl aldehyde, 4-6 parts by weight of skeletal nickel or skeletal copper or a mixture thereof, 100 parts by weight of pure water washing liquor with pH = 7.5-8 into a high-pressure reaction kettle, and stirring the reaction kettle at a constant speed of 500r/h under a nitrogen atmosphere of 0.2 MPa; the weight ratio of the framework metal to the n-butyraldehyde is 1: 10-1: 100, respectively;
step 2, reacting at the temperature of less than or equal to 25 ℃ for 1 hour under normal pressure, slowly heating to 35 ℃, reacting for 0.5 hour, slowly heating to 60 ℃ for reacting for 0.5 hour, slowly heating to 90 ℃ for reacting for 0.5 hour, and rapidly cooling to below 35 ℃ in a cooling water environment;
and 3, replacing three times with 0.2MPa hydrogen, introducing liquid ammonia or dimethylamine, wherein the feeding molar ratio of the liquid ammonia or dimethylamine to the n-butyl aldehyde is more than or equal to 0.55: 1, filling hydrogen, boosting the pressure to (and keeping) 3.0MPa, increasing the stirring speed to 700 r/h, heating to 90 ℃ to activate the reaction, and keeping for 0.5h after no hydrogen is absorbed;
and 4, filtering the mother liquor, recovering the catalyst, distilling off ammonia gas at normal pressure, and rectifying and collecting fractions at 155-156 ℃.
2. The method of synthesis according to claim 1, characterized in that: the weight ratio of the framework metal to the n-butyraldehyde is 1: 20-1: 60.
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| GB728702A (en) * | 1951-12-31 | 1955-04-27 | Ruhrchemie Ag | Process for the production of amines |
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| CN1962604A (en) * | 2006-11-29 | 2007-05-16 | 建德市新化化工有限责任公司 | Method for synthesis of orthooctylamine |
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| CN101880221A (en) * | 2010-06-22 | 2010-11-10 | 上海师范大学 | Process for preparing octenal by one-pot method |
| CN108603038A (en) * | 2016-02-02 | 2018-09-28 | Ａｇｃ株式会社 | Near infrared absorbing coloring matter, optical filter and photographic device |
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| GB728702A (en) * | 1951-12-31 | 1955-04-27 | Ruhrchemie Ag | Process for the production of amines |
| CN1554640A (en) * | 2003-12-24 | 2004-12-15 | 建德市新化化工有限责任公司 | Process for synthesizing iso octyl amine |
| CN1984873A (en) * | 2004-05-13 | 2007-06-20 | 巴斯福股份公司 | Method for the continuous production of an amine |
| CN1962604A (en) * | 2006-11-29 | 2007-05-16 | 建德市新化化工有限责任公司 | Method for synthesis of orthooctylamine |
| CN101880221A (en) * | 2010-06-22 | 2010-11-10 | 上海师范大学 | Process for preparing octenal by one-pot method |
| CN108603038A (en) * | 2016-02-02 | 2018-09-28 | Ａｇｃ株式会社 | Near infrared absorbing coloring matter, optical filter and photographic device |
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Denomination of invention: The synthesis method of isooctylamine and its derivatives by one pot method Granted publication date: 20240202 Pledgee: Weifang Jinma road sub branch of Bank of Weifang Co.,Ltd. Pledgor: JIAYIJIA BIOTECH Inc. Registration number: Y2024980037507 |
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