CN101360704B - Method for the production of aminoalkane acid amides - Google Patents
Method for the production of aminoalkane acid amides Download PDFInfo
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- CN101360704B CN101360704B CN2006800511161A CN200680051116A CN101360704B CN 101360704 B CN101360704 B CN 101360704B CN 2006800511161 A CN2006800511161 A CN 2006800511161A CN 200680051116 A CN200680051116 A CN 200680051116A CN 101360704 B CN101360704 B CN 101360704B
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- 150000001408 amides Chemical class 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 50
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 81
- 238000005984 hydrogenation reaction Methods 0.000 claims description 36
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000009435 amidation Effects 0.000 description 24
- 238000007112 amidation reaction Methods 0.000 description 24
- 239000000376 reactant Substances 0.000 description 24
- -1 cyanic acid alkanoyl halogen Chemical class 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000564 Raney nickel Inorganic materials 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- ZLHYDRXTDZFRDZ-UHFFFAOYSA-N epsilon-aminocaproamide Chemical compound NCCCCCC(N)=O ZLHYDRXTDZFRDZ-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229950010765 pivalate Drugs 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XZUDGZXKOFPLBC-UHFFFAOYSA-N 5-cyanopentanamide Chemical compound NC(=O)CCCCC#N XZUDGZXKOFPLBC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 description 1
- BHPYMZQTCPRLNR-UHFFFAOYSA-N 2-cyanoethanethioamide Chemical class NC(=S)CC#N BHPYMZQTCPRLNR-UHFFFAOYSA-N 0.000 description 1
- NICLKHGIKDZZGV-UHFFFAOYSA-N 2-cyanopentanoic acid Chemical compound CCCC(C#N)C(O)=O NICLKHGIKDZZGV-UHFFFAOYSA-N 0.000 description 1
- JDEFPFLTCXIVDH-UHFFFAOYSA-N 2-cyanopropanoic acid Chemical compound N#CC(C)C(O)=O JDEFPFLTCXIVDH-UHFFFAOYSA-N 0.000 description 1
- MVEPJLNIXKEKMI-UHFFFAOYSA-N 4-aminobutanamide;hydrochloride Chemical compound Cl.NCCCC(N)=O MVEPJLNIXKEKMI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- RSDAEJUBONORIX-UHFFFAOYSA-N amino 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)ON RSDAEJUBONORIX-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 230000001914 calming effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- AEDIXYWIVPYNBI-UHFFFAOYSA-N heptanamide Chemical compound CCCCCCC(N)=O AEDIXYWIVPYNBI-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Preparation of aminoalkanoic acid amide comprises reaction of cyanoalkanoic acid ester with (a) at least a mol-equivalent of ammonia or amine, and (b) hydrogen in the presence of catalyst, at increased pressure, where optionally the formed intermediate stages are not isolated and the reaction with (b) takes place simultaneously or less than 100 minutes, after the beginning of the reaction of cyanoalkanoic acid ester with (a).
Description
The present invention relates to through making cyanic acid alkanoates and a) ammonia or amine and b) hydrogen reacts the method for preparing aminoalkane acid amides in the presence of catalyzer, do not separate any midbody and and the components b that are generated) reaction and the cyanic acid alkanoates that carry out and component reaction a) begins simultaneously or begin back beginning in maximum 100 minutes at it the latest.
The reaction of carboxylic acid or carboxylicesters and ammonia (amidation) is known in principle.For example, DE-2026832 has described the method for preparing carboxylic acid amides, and saturated and unsaturated carboxylic acid or its ester of straight chain and side chain and ammonia are reacted in the presence of catalyzer.Appropriate catalyst is the metallic compound of compound, particularly titanium, zirconium and tantalum of IVb and the Vb family metal of the periodic table of elements (PTE) that dissolves in reaction mixture.DE-A 21 10 060 has described and has used aliphatic, the alicyclic or mixed aliphatic series/cycloaliphatic amines of primary and secondary to replace ammonia to prepare the correlation method of N-replacement carboxylic acid amides.
The preparation of aminoalkane acid amides also is known.As far back as 1934, DE-A 597 305 just described cyanic acid alkanamides (especially Cyanothioacetamide derivatives) through the conversion of catalytic hydrogenation to corresponding aminoalkane acid amides.The cyanic acid alkanamides prepares through corresponding cyanic acid alkanoyl halogen and ammonia or amine are reacted in (separately) reactions step before.People such as G.D.Buckley (J.Chem.Soc. (chemistry meeting will) 1947; The the 1500th to 1503 page) point out; At catalyzer (Raney nickel catalyst for example; Hereinafter is also referred to as Ra-Ni, or as another instance, at the palladium on the lime carbonate) in the presence of produce corresponding aminoalkane acid amides with hydrogen reducing 2-4-nitro alkyl cyanogen.
At US 4,780, another method has been described in 542, according to this method, at first in water medium, acid is changed into acid anhydrides with alkyl chloroformate, this acid anhydrides subsequently can with the alcohol reaction with produce ester or with the amine reaction to produce aminoalkane acid amides.
In WO 01/77068, having described 5-cyanovaleramide and hydrogen reacts in the presence of catalyzer to produce the 6-aminocaproamide.Raw material (5-cyanovaleramide) is preparing in the reactions step separately again in advance; For example, it can prepare through corresponding cyanopentanoic acid ester and ammonia are reacted in the presence of alcohol.In DE-A29 47 825, similar approach has been described, according to this method, through in the presence of inert solvent, noble metal catalyst and the hydrogenchloride under reaction conditions under 5 to 80 ℃ temperature hydrogenation 3-cyanic acid propionic acid amide, preparation 4-amino-butanamide hydrochloride.Used reactant (3-cyanic acid propionic acid amide) can be prepared through partly hydrolysed by corresponding dintrile.
US-A 3,235, and 576 relate to the method for preparing the omega-amino-hexanamide.At this used starting compound is 7-cyanic acid-2, the methyl esters of 5-heptadienoic acid, and it at first produces corresponding amide with H-H reaction.In first hydrogenation, for example, use palladium catalyst, prepare corresponding 7-cyanic acid heptamide and isolating midbody is changed into corresponding omega-amino-hexanamide in use contains second hydrogenation of cobalt and nickeliferous catalyzer.Perhaps, can be raw material also with corresponding unsaturated amides.
DE-A 26 01 462 relates to the two-step approach that is used to prepare the 6-aminocaproamide, 5-cyanopentanoic acid ester and excess ammonia is being contained in second step of reaction in the presence of cobalt and/or the nickeliferous loaded catalyst through reaction in 2 to 6 hours and with formed midbody be hydrogenated to the 6-aminocaproamide.The reaction of ester and ammonia) and need not separate formed midbody (cyanic acid alkanamides) DE-A 26 01 462 points out really, can in fact in the presence of catalyzer required in second reactions step (hydrogenation: the cyanic acid alkanamides is to the conversion of aminoalkane acid amides), carry out (the amidation: of first reactions step in principle.But, can not find out that from DE-A 26 01 462 or from any other prior art document the amidation and the hydrogenation of raw material (cyanic acid alkanoates) can be carried out simultaneously, or hydrogenation can directly be carried out after amidation.All related art documents point out that first reactions step (amidation) must fully be carried out so that the midbody (cyanic acid alkanamides) that forms is hydrogenated to aminoalkane acid amides in second reactions step through at least 2 hours.
On the contrary, DE-A 26 01 461 relates to the method for preparing omega-amino-alkanoic acid alkyl ester, and wherein ω-cyanic acid alkanoic acid alkyl ester uses ammonia hydrogenation in the presence of load-type nickel and/or cobalt catalyst under temperature that raises and elevated pressure.In the method, cyanic acid is hydrogenated to corresponding amine thus, but does not carry out amidation, because the ester official of starting substance can also keep.
The purpose of this invention is to provide through making cyanic acid alkanoates and a) ammonia or amine and b) hydrogen reacts the novel method for preparing aminoalkane acid amides in the presence of catalyzer.
According to the present invention; Through the cyanic acid alkanoates under the elevated pressure and a) at least one molar equivalent ammonia or at least one molar equivalent amine and b) hydrogen reacts in the presence of catalyzer and realizes this purpose, do not separate any midbody and and the components b that are generated) and reaction and cyanic acid alkanoates and component reaction a) begins simultaneously or begin back beginning in maximum 100 minutes at it the latest.
The advantage of method of the present invention is that it is compared more rapidly with the method for from prior art, knowing and carries out.For example, amidation and hydrogenation do not require the change catalyzer; In fact, carry out simultaneously and/or spatially separately carry out if amidation and hydrogenation are non-, amidation also can realize under the situation that does not have catalyzer.
In addition, method of the present invention is with preferably at least 95%, and more preferably at least 98%, preferred at least 99% highly selective provides required product (aminoalkane acid amides) especially.
In one embodiment of the invention, the advantage of method of the present invention is, from reaction product (aminoalkane acid amides), removes and reclaim unconverted component a) (ammonia or amine).Especially in continuous processing, this can be recycled in the reaction circuit valuable reactant.In this embodiment, another advantage is, because preferred selected component a) removes condition, can further improve product selectivity.
Another advantage can be considered to, and when fixed bed catalyst (especially fixed bed carried type catalyzer) was used in hydrogenation, reaction product only contained the catalyst metal of few trace, so that can finally purify through crystallization.In traditional method, must filter and remove catalyzer, and product must distill purification, because the metal trace that exists in final product infringement product stability and product characteristics (possible ligand effect).In addition, the required condition of distillation causes low product yield.
Suitable reactant is all common cyanic acid alkanoatess in principle; If suitably, also can use the mixture of two kinds or more kinds of cyanic acid alkanoatess, but preferably use a kind of cyanic acid alkanoates.If suitably, also can use compound with two or more cyanic acid and/or two or more ester groups.But preferred reactant per molecule has a cyanic acid and an ester group.If suitably, replace ester group, also can use corresponding molecule with an acidic group.The instance of cyanic acid alkanoates is the methyl esters or the ethyl ester of cyanoacetic acid, cyanopropionic acid, cyano butyric acid, cyanopentanoic acid or cyanic acid caproic acid, and cyanic acid is preferably on the terminal carbon of fundamental chain alkanoic acid.If basic paraffinic acid structure can have other substituting group, preferably one or two C suitably,
1-C
3-alkyl, particularly two methyl substituents.Preferred cyanic acid alkanoates comprises cyanic acid having 4 to 10 carbon atoms with carbon atom ester group, and the cyanic acid official can be on the terminal carbon of basic paraffinic acid skeleton.Particularly preferably be 2-cyanic acid-2,2-dimethyl acetic acid methyl esters or corresponding ethyl ester.
The cyanic acid alkanoates with at least one molar equivalent component a), preferably at 2 to 30 times of molar excess, more preferably a) down amidation of the component of 5 to 25 times of molar excess.When the many ester officials in the reactant can be by amidation, must corresponding increase component amount a).
Suitable component is ammonia or amine a); If suitably, also can use mixture.But, preferably only use a kind of component a), particularly ammonia.When using amine, suitable amine is monoalkyl-or dialkylamine (to obtain corresponding monoalkylation or dialkylated acid amides), particularly methylamine or n n dimetylaniline particularly.
In the preferred embodiment of method of the present invention, used reactant is a 2-cyanic acid-2,2-dimethyl acetic acid methyl esters, and used component is an ammonia a).
Reactant, midbody that particularly in amidation, obtains (cyanic acid alkanamides) and hydrogen (components b); Hydrogenation) reaction in the presence of catalyzer.Appropriate catalyst is all hydrogenation catalysts well known by persons skilled in the art in principle.Catalyzer for example can be, sponge catalysts, loaded catalyst, thin layer catalyst or supported catalyst not, preferred negative supported catalyst.Catalyzer is preferably with the fixed bed catalyst form, and particularly the loaded catalyst form exists.Preferred catalyst comprises at least a VII and VIII family precious metal, preferred cobalt (Co) and nickel (Ni), and the optional at least a metal that is selected from copper, manganese, chromium or iron.When working load type catalyzer, carrier can be selected from the common metal oxide compound, the mixture of aluminum oxide, zirconium white, silicon-dioxide or these MOXs for example, and preferably aluminum oxide and zirconium white particularly preferably are zirconium white.The instance of preferred catalyst is that Raney cobalt catalyzer (hereinafter is known as Ra-Co) or Raney nickel catalyst-such catalyzer can be used as multi-form commodity with Raney
TMCobalt or Raney
TMThe nickel acquisition of running after fame.Other instance of preferred catalyst is the loading type hydrogenation catalyst of being processed by nickel oxide, powder blue, cupric oxide and zirconium white, if suitably, it can also comprise other metal component.Appropriate catalyst can be for example available from people such as document Mozingo with these Preparation of catalysts methods; Organic Synth.Coll. (organic synthesis intersection) volume 3; The 181st page and following pages; Fieser and Fieser, Reagents for Org.Synth. (organic synthesis reagent) rolls up 1, the 723-731 page or leaf, EP-A 0 963 975 or EP-A 1 106 600.
The cyanic acid alkanoates to the conversion of corresponding aminoalkane acid amides in elevated pressure, preferably at 10 to 250 crust, more preferably at 50 to 220 crust, particularly preferably in carrying out under 80 to 210 crust.If suitably, reaction also can be carried out under standardpressure.Temperature can be 20 to 150 ℃, preferred 60 to 150 ℃, and more preferably 80 to 120 ℃, preferred especially 80 to 110 ℃.
Method of the present invention is carried out as follows: reactant (cyanic acid alkanoates) and component a) and components b) reaction begin simultaneously or and components b) the reactant that is reflected at begin the back with component reaction a) and began in maximum 100 minutes.Preferably carry out method of the present invention as follows: reactant and components b) be reflected at reactant and component reaction a) begin back beginning in maximum 100 minutes.
Under the situation of second kind of selection, with components b) reaction therefore carried out behind the maximum delay time at 100 minutes.The preferred time of lag of selecting 5 to 100 minutes.Do not separate formed any midbody.Crucial is, add component a) or component a) with reactant reaction before, not with components b) add in the reactant because the amidation of amino-alkane acid esters is only carried out with minute quantity as side reaction.When hydrogenation was not carried out with the amidation of cyanic acid alkanoates simultaneously, can infer formed midbody mainly was corresponding cyanic acid alkanamides.
When said hydrogenation just began after amidation begins, hydrogenation was more preferably than late 5 to 60 minutes (5 to 60 minutes time of lag) of amidated beginning.Particularly preferably be 8 to 20 minutes time of lag.
In one embodiment of the invention, component a) and b) progressively be fed in the reactant.Especially, this method is used in batch process, charging a) hydrogen then of component at first progressively in cyanic acid alkanoates solution.This embodiment more preferably is used in the autoclave.
After amidation begins, just begin and it equally preferably is used in another embodiment in the autoclave in said hydrogenation, catalyzer, cyanic acid alkanoates solution (reactant) and the component of at first when initial, under the peak pressure of 10 crust, packing into a) and a part of hydrogen.In this process, the maximum temperature of 60 ℃ of should exceeds not; Temperature is preferably 20 to 30 ℃.Subsequently, temperature is risen to 70 to 150 ℃, preferred 75 to 120 ℃ of maximums, and through further interpolation hydrogen hydrogen pressure are risen to 50 to 210 crust.The rising of hydrogen pressure and temperature can simultaneously or be carried out in succession.Preferably, at first slow elevated temperature, and after temperature reaches required end value (greater than 70 ℃), inject hydrogen to required resulting pressure value (greater than 50 crust) rapidly.Begin during at least 50 crust, to count time of lag at least 70 ℃ and hydrogen pressure from reactant solution and component merging a) at this to temperature.
Perhaps, this embodiment also can only be packed reactant solution and component when initial into a) with catalyzer and after the beginning that heats up, just add hydrogen and carry out.Also begin during at least 50 crust, to count time of lag at least 70 ℃ and hydrogen pressure in the case to temperature from reactant and component merging a).Also can arrive the completion that heats up and just adding hydrogen.
In another embodiment of method of the present invention, especially in semi-batch or continuous processing,, spatially be separated from each other and carry out amidation and hydrogenation through upper reaches connection delay time zone.Under the situation in this time of lag of zone, be meant time of lag per unit volume zone time of lag reactant hourly, component a) with solvent TV (t=Vol
R+ Vol
a+ Vol
S)/Vol
DT/ 1 hour).In this case, a) (preferred ammonia) can be before they arrive actual hydrogenation reactor for the appropriate reaction thing of continuously feeding and component separately, reaction when they are regional through time of lag.The zone also may reside in being equipped with of hydrogenation reactor and had only material of low catalytic activity (if any) (for example steel loop, steatite etc.) or temperature to keep below in the section of the required threshold temperature of hydrogenation this time of lag.
When amidation and hydrogenation spatially are separated from each other when carrying out by connection delay time zone, the upper reaches, the temperature in this zone is 20 to 100 ℃ time of lag, preferred 30 to 60 ℃.Through behind this zone,, more preferably carry out hydrogenation under 75 to 120 ℃ the temperature at preferred 60 to 150 ℃ time of lag.Amidation and hydrogenation also can be carried out under the uniform temp in 20 to 150 ℃ of scopes if suitably.
The amine that in the hydrogenation of nitrile, forms can with the reactant ester group when intramolecularly or the intermolecular reaction, or when hydrogenation will be carried out under being unfavorable for amidated condition, this program was favourable.Therefore previous embodiments is favourable in the time will relative long-chain cyanic acid alkanoates being changed into corresponding aminoalkane acid amides especially.
This method can be in solvent; For example in alcohol or N-Methyl pyrrolidone (NMP); Preferably at the monobasic fatty alcohol, more preferably single step is carried out in the alcohol that is selected from methyl alcohol (MeOH), ethanol (EtOH), propyl alcohol (PrOH), i-PrOH, 1-butanols (1-BuOH), 2-BuOH, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol.Solvent can be with 5 to 95% [weight %] in reaction mixture, and is preferred 20 to 70%, and more preferably 30 to 60% ratio is used.
As stated, this method can with in batches, semi-batch or continuous mode carry out preferred successive reaction.Product can separate and purifies through distillation or crystallization or both combinations.Preferably crystallization.When especially in the presence of fixed bed catalyst, carrying out step of hydrogenation, can carry out crystallization, because product in the case only has the metal of the very trace that exists in the catalyzer as impurity.
In another preferred form of the present invention, methyl cyanic acid ester is being gone up hydrogenation and is being changed into acid amides simultaneously at Raney nickel (5 weight %) under 100 ℃ in the autoclave in batches in the presence of the 7 equivalent liquefied ammonia as 50% solution in the 2-butanols.Filtration removes catalyzer, and the fractionation by distillation product.
One of advantage of comparing with sponge catalysts as the loading type hydrogenation catalyst of fixed bed catalyst is better anti-washing out property of metals ion.In the special preferred embodiment of this method; Methyl cyanic acid ester merges (ester changes into acid amides) as 40% solution and 10 to the 25 equivalent ammonia in MeOH in the tubular reactor of replacement is housed; And under 80 to 120 ℃ and 150 to 250 crust after time of lag of 8 to 20 minutes, by 20%NiO, 28%CoO, 13%CuO and 31%ZrO
2Hydrogenation on the loading type hydrogenation catalyst of processing.Through the single step crystallization, from crude solution, isolate product.
In another embodiment of the present invention, with components b) reaction (hydrogenation) after, remove unconverted component a) (promptly as yet not with the ammonia or the amine moiety of cyanic acid alkanoates reaction).Preferably being lower than 150 ℃,, especially preferably be lower than under 110 ℃ the temperature and remove unconverted component a) more preferably less than 130 ℃.
In another embodiment of the present invention, preferably than with components b) reaction (hydrogenation) in the low temperature of temperature under remove unconverted component a).Preferably being lower than 150 ℃,, especially preferably be lower than under 110 ℃ the temperature and remove unconverted component a) more preferably less than 130 ℃.
Also preferably remove step itself (from reaction mixture, removing unconverted component a)) as soon as possible.In the present invention, term " fast as far as possible " should be understood that to be meant that removing step itself continues maximum 300 minutes, more preferably maximum 200 minutes, and especially preferred maximum 120 minutes.
Preferably under relatively lower temp He as soon as possible, remove unconverted component a).
In another embodiment, especially in continuous processing, in isolated system, remove unconverted component a).Isolated system should be understood that to be meant any unit that removes well known by persons skilled in the art, especially adds tower of calming the anger (Druckgaskolonne) or distillation tower.This means comprise product (aminoalkane acid amides) if, unconverted component a) with suitably, the known by one of skill in the art method of the reaction mixture of solvent is transferred to and is removed the unit from carrying out the hydrogenant device.Preferably being lower than 150 ℃,, especially preferably be lower than under 110 ℃ the temperature and from remove the unit, remove unconverted component a) more preferably less than 130 ℃.In removing the unit, remove unconverted component a) time, the residence time of aminoalkane acid amides (product) is preferably 1 to 300 minute, and more preferably 1 to 200 minute, especially preferred 1 to 120 minute.
From reaction mixture, removing unconverted component (a) as soon as possible is favourable according to finding; Especially because amidation is balanced reaction; When removing amine or ammonia at elevated temperatures continuously from reaction mixture, it can move in the ester direction, and for reacting the enough time that provides relatively slowly.
Therefore, in the aftertreatment of the aminoalkane acid amides that in alcoholic solution for example, exists, reversed reaction can take place to produce corresponding esters of (one or more) alcohol that exists in the reaction mixture when from mixture, removing used ammonia or amine at elevated temperatures.So importantly, in removing, keep alap temperature and/or the residence time of aminoalkane acid amides (product) in removing unit (for example adding calm the anger tower or distillation tower) minimized.
With reference to the following example the present invention is described:
Embodiment:
Autoclave test:
Summary
In autoclave, pack into when initial reactant and catalyzer, and through nitrogen purging with the component inerting.Subsequently, inject 5 crust hydrogen.Be metered into the ammonia of aequum, then autoclave under agitation slowly be heated to temperature of reaction (80 ℃).This step spends average 90 minutes, and be about 90 minutes the time of lag of the reactant solution that promptly contacts with ammonia.After reaching temperature of reaction, inject specified pressure in hydrogen to the following table 1 rapidly, and through under pressure-controlling, in experimental period, being metered into, the hydrogen that replacement is consumed is until writing down less than further absorption of hydrogen.
In 2.5 liters of autoclaves, carry out autoclave test, this autoclave has tubular shaft agitator disk (the about 600rpm of stirring velocity), electrically heated and sheath air cooling, 2 baffle plates, sprays and introduce hydrogen via the tubular shaft whisking appliance through the autoclave lid.To 10% water humidity, proofread and correct Raney catalyst weight, that is, in fact, weigh up than specified and Duo 10% water moist catalysis.Via vapor-phase chromatography (GC) (condition: 60m DB1701; 0.32 millimeter of internal diameter; 0.25 micron of film thickness; Detector: FID; Temperature program(me): 80 ℃ → 10K/ minute → 280 ℃, 40 minutes, splitting ratio 100: 1, carrier gas helium) analytical reaction elute and form with weight % report.
Through vapor-phase chromatography with interior mark (I.S.) (I.S. piperidines; Thus obtained concentration in rough elute multiply by rough elute total mass, and the yield that will calculate thus and theoretical yield compare) assaying reaction device yield.The 2-cyanic acid-2 of purity＞99.8% is all used in reaction, and 2-dimethyl acetic acid methyl esters carries out.The gained primary product is amino pivalyl amine (3-amino-2, a 2-dimethyl propylene acid amides).
These embodiment show, can realize at least 90% extraordinary selectivity with Raney nickel and Raney cobalt.The amount of ammonia is high more, and catalyst concn is high more and hydrogen pressure is high more, and selectivity is good more.In embodiment 8, carry out metal assay, in reaction effluent, find the Co of 430ppm.
Experiment continuously:
Summary
Be furnished with solvent, ammonia and nitrile ester fresh feed pump, 250 milliliters of steel loops be housed in bottom and upper reactor section and 500 milliliters of hydrogenation catalyst sheets (5 * 3 millimeters) with following composition be housed: 28%NiO, 28%CoO, 13%CuO and 31%ZrO in central authorities
21 liter of reactor drum (10 * 2000 millimeters) in the liquid phase pattern embodiment that experimentizes.The reducing program of catalyzer is following: with reactor drum under 50 liters/hour hydrogen feed at 5 hours internal heating to 180 ℃; Kept 20 hours with 50 liters of/hour hydrogen down at 180 ℃ then; Cooling and purge with MeOH under hydrogen adds ammonia and reactant and solvent then.Steel loop at reactor lower part serves as amidated time of lag of zone.Used adds 11 equivalent hydrogen whenever measuring nitrile.Be about 10 minutes time of lag thus.
Embodiment 9
503 grams per liter MeOH and as the 2-cyanic acid-2 of nitrile ester, 2-dimethyl acetic acid methyl esters (weight ratio 1: 1) and 670 gram ammonia (based on the nitrile ester, 20 equivalent ammonia) 200 crust with 100 ℃ down conveying pass through reactor drum.Volume space velocity is 0.5 kg/liter * hour.Elute analysis revealed (solvent-freely calculate) 99.89% amino pivalyl amine, 0.03% amino methyl pivalate and 0.08% other.Be about 9.8 minutes time of lag.
Embodiment 10
With 250 grams per liter THFs (THF) with as the 2-cyanic acid-2 of nitrile ester, 2-dimethyl acetic acid methyl esters (weight ratio 70: 30) and 205 gram ammonia (based on the nitrile ester, 20 equivalent ammonia) 200 crust with 100 ℃ down conveying pass through reactor drum.Volume space velocity is 0.15 kg/liter * hour.Elute analysis revealed (solvent-freely calculate) 33.083% amino pivalyl amine, 65.68% amino methyl pivalate and 0.49% other.Be about 27 minutes time of lag.
Can find out; Can be with the almost completely amidation of nitrile ester (staying 0.03% amino methyl pivalate) in as the MeOH of the instance of monobasic fatty alcohol, even carry out simultaneously and also like this under the high volume space velocity (based on solvent-free nitrile ester) at 0.5 kg/liter * hour in the embodiment that amidation is more slowly carried out in THF in the amidation of reactant and hydrogenation.Even under 0.15 kg/liter * hour low volume space velocity, still have about 34% nitrile ester by amidation to produce the mixture of about 66% amino pivalate and amino pivalyl amine.The former no longer changes into acid amides under reaction conditions.
Claims (22)
1. one kind through making the cyanic acid alkanoates at the pressure of 10 to 250 crust down and a) at least one molar equivalent ammonia or at least one molar equivalent amine and b) hydrogen reacts the method for preparing aminoalkane acid amides in the presence of catalyzer, wherein do not separate any midbody and and the components b that are generated) reaction and cyanic acid alkanoates and component reaction a) begins simultaneously or begin to begin in afterwards maximum 100 minutes at it the latest.
According to the process of claim 1 wherein cyanic acid alkanoates and component a) and b) reaction begin simultaneously.
3. according to the process of claim 1 wherein that the cyanic acid alkanoates at first a) reacts with component, and formed midbody directly and components b) reaction.
4. according to the method for claim 3, wherein said reaction through progressively add component a) and b) carry out.
5. according to the method for claim 4, wherein at first pack into catalyzer and cyanic acid alkanoates and component solution a) are no more than 60 ℃ maximum temperature, then, are adding under the hydrogen, and pressure is risen to 80 to 210 crust and temperature is risen to 80 to 150 ℃.
6. according to the method for claim 5, the hydrogen partial of wherein at first under the peak pressure of 10 crust, packing into.
7. according to the method for claim 3, wherein by upper reaches connection delay time zone, spatially carry out apart from each other cyanic acid alkanoates and component a) and b) reaction.
8. according to the method for claim 7, wherein the temperature in the time of lag of the zone is 20 to 100 ℃, and the temperature in the hydrogenation is 60 to 150 ℃.
9. according to the method for claim 1 or 3, wherein used cyanic acid alkanoates is a 2-cyanic acid-2,2-dimethyl acetic acid methyl esters.
10. according to the method for claim 1 or 3, wherein used component is an ammonia a).
11. according to the method for claim 1 or 3, wherein said catalyzer exists with the form of fixed bed catalyst.
12. according to the method for claim 1 or 3, wherein said catalyst pack is nickeliferous, cobalt, copper and zirconium.
13., carry out under the wherein said existence that is reflected at solvent according to the method for claim 1 or 3.
14. according to the method for claim 1 or 3, wherein with components b) be reflected at time of lag of 8 to 20 minutes after begin.
15. according to the method for claim 1 or 3, wherein after the reaction in the presence of the fixed bed catalyst, the gained aminoalkane acid amides passes through crystallization and purification.
16. according to the method for claim 1 or 3, wherein with components b) reaction after be lower than under 130 ℃ the temperature and removing unconverted component a).
17. according to the method for claim 1 or 3, wherein with components b) reaction after remove unconverted component a), this remove than with components b) reaction in the low temperature of temperature under carry out or remove step in maximum 300 minutes, carrying out.
18., wherein remove being lower than under 110 ℃ the temperature, or in maximum 120 minutes, carry out said removing according to the method for claim 17.
19., wherein in isolated system, carry out said removing according to the method for claim 16.
20. according to the method for claim 19, wherein in the component of the at first conversion in isolated system removing a), the residence time of aminoalkane acid amides is 1 to 120 minute.
21. according to the method for claim 13, wherein said solvent is the monobasic fatty alcohol.
22. according to the method for claim 19, wherein said isolated system is to add calm the anger tower or distillation tower.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200510060803 DE102005060803A1 (en) | 2005-12-20 | 2005-12-20 | Preparation of aminoalkanoic acid amide comprises reaction of cyanoalkanoic acid ester with at least a mol-equivalent of ammonia or amine, and hydrogen in the presence of catalyst |
| DE102005060803.5 | 2005-12-20 | ||
| EP06115783.0 | 2006-06-21 | ||
| EP06115783 | 2006-06-21 | ||
| PCT/EP2006/069777 WO2007071626A2 (en) | 2005-12-20 | 2006-12-15 | Method for the production of aminoalkane acid amides |
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| Publication Number | Publication Date |
|---|---|
| CN101360704A CN101360704A (en) | 2009-02-04 |
| CN101360704B true CN101360704B (en) | 2012-10-17 |
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| CN2006800511161A Expired - Fee Related CN101360704B (en) | 2005-12-20 | 2006-12-15 | Method for the production of aminoalkane acid amides |
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| DE (1) | DE102005060803A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3235576A (en) * | 1958-07-29 | 1966-02-15 | Montedison Spa | Process for preparing the amide of omega-aminocaprylic acid and amide product |
| US4119665A (en) * | 1976-01-16 | 1978-10-10 | Basf Aktiengesellschaft | Manufacture of 6-aminocaproamide |
-
2005
- 2005-12-20 DE DE200510060803 patent/DE102005060803A1/en not_active Withdrawn
-
2006
- 2006-12-15 CN CN2006800511161A patent/CN101360704B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3235576A (en) * | 1958-07-29 | 1966-02-15 | Montedison Spa | Process for preparing the amide of omega-aminocaprylic acid and amide product |
| US4119665A (en) * | 1976-01-16 | 1978-10-10 | Basf Aktiengesellschaft | Manufacture of 6-aminocaproamide |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102005060803A1 (en) | 2007-06-28 |
| CN101360704A (en) | 2009-02-04 |
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