JP6843141B2 - 部分的にN−ヒドロキシエチル化されたtert−1,6−ヘキサンジアミンの改善された合成方法 - Google Patents
部分的にN−ヒドロキシエチル化されたtert−1,6−ヘキサンジアミンの改善された合成方法 Download PDFInfo
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- JP6843141B2 JP6843141B2 JP2018530775A JP2018530775A JP6843141B2 JP 6843141 B2 JP6843141 B2 JP 6843141B2 JP 2018530775 A JP2018530775 A JP 2018530775A JP 2018530775 A JP2018530775 A JP 2018530775A JP 6843141 B2 JP6843141 B2 JP 6843141B2
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- hexanediamine
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- hydroxyethyl
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- 230000015572 biosynthetic process Effects 0.000 title description 32
- 238000003786 synthesis reaction Methods 0.000 title description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 124
- 238000006243 chemical reaction Methods 0.000 claims description 73
- 150000001875 compounds Chemical class 0.000 claims description 64
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 29
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- -1 hydroxyethyl group Chemical group 0.000 claims description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 16
- FVHWBLOAJUDPQQ-UHFFFAOYSA-N 2-[6-[2-hydroxyethyl(methyl)amino]hexyl-methylamino]ethanol Chemical compound OCCN(C)CCCCCCN(C)CCO FVHWBLOAJUDPQQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 230000011987 methylation Effects 0.000 claims description 8
- 238000007069 methylation reaction Methods 0.000 claims description 8
- 150000003335 secondary amines Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- LRKJBUYVTSALAA-UHFFFAOYSA-N 2-[6-(2-hydroxyethylamino)hexylamino]ethanol Chemical compound OCCNCCCCCCNCCO LRKJBUYVTSALAA-UHFFFAOYSA-N 0.000 claims description 3
- KWHPSVXVBZIQLO-UHFFFAOYSA-N 2-[6-[bis(2-hydroxyethyl)amino]hexylamino]ethanol Chemical compound OCCNCCCCCCN(CCO)CCO KWHPSVXVBZIQLO-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- VCSLWHMUQFZNRA-UHFFFAOYSA-N 2-(6-aminohexylamino)ethanol Chemical compound NCCCCCCNCCO VCSLWHMUQFZNRA-UHFFFAOYSA-N 0.000 claims description 2
- 230000001035 methylating effect Effects 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 2
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid group Chemical group C(CCCCC(=O)O)(=O)O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 42
- 239000001361 adipic acid Substances 0.000 description 28
- 235000011037 adipic acid Nutrition 0.000 description 28
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 16
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical group O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- MDKQJOKKKZNQDG-UHFFFAOYSA-N n,n'-dimethylhexane-1,6-diamine Chemical compound CNCCCCCCNC MDKQJOKKKZNQDG-UHFFFAOYSA-N 0.000 description 11
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical group COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 10
- FKQWHDDVHURHNJ-UHFFFAOYSA-N 3,8-diaminooctan-1-ol Chemical compound NCCCCCC(N)CCO FKQWHDDVHURHNJ-UHFFFAOYSA-N 0.000 description 9
- 238000006482 condensation reaction Methods 0.000 description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical group OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000001308 synthesis method Methods 0.000 description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 6
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 230000037361 pathway Effects 0.000 description 5
- 150000003512 tertiary amines Chemical group 0.000 description 5
- 238000007039 two-step reaction Methods 0.000 description 5
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 3
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- MEJQLVORSPSJDX-UHFFFAOYSA-N N,N'-dimethylhexane-1,6-diimine Chemical compound CN=CCCCCC=NC MEJQLVORSPSJDX-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001408 amides Chemical group 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 3
- 229910000103 lithium hydride Inorganic materials 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- CKCCHKQRHWOCLZ-UHFFFAOYSA-N 2-[6-[bis(2-hydroxyethyl)amino]hexyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCCCCCN(CCO)CCO CKCCHKQRHWOCLZ-UHFFFAOYSA-N 0.000 description 2
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 125000004420 diamide group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- OYFWLCJAPSAGCG-UHFFFAOYSA-N n'-methylhexane-1,6-diamine Chemical compound CNCCCCCCN OYFWLCJAPSAGCG-UHFFFAOYSA-N 0.000 description 2
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- HIXRCLYXOZHPNU-UHFFFAOYSA-N 2-(2-hydroxyethyl)hexanediamide Chemical compound NC(=O)CCCC(C(N)=O)CCO HIXRCLYXOZHPNU-UHFFFAOYSA-N 0.000 description 1
- CVVKXSUKUQSIHH-UHFFFAOYSA-N 2-[6-(dimethylamino)hexyl-(2-hydroxyethyl)amino]ethanol Chemical compound CN(C)CCCCCCN(CCO)CCO CVVKXSUKUQSIHH-UHFFFAOYSA-N 0.000 description 1
- BVSCHPOVXVHISP-UHFFFAOYSA-N 2-[6-(dimethylamino)hexyl-methylamino]ethanol Chemical compound CN(C)CCCCCCN(C)CCO BVSCHPOVXVHISP-UHFFFAOYSA-N 0.000 description 1
- ZHHBGWTZQAGXNO-UHFFFAOYSA-N 2-[6-[bis(2-hydroxyethyl)amino]hexyl-methylamino]ethanol Chemical compound CN(CCCCCCN(CCO)CCO)CCO ZHHBGWTZQAGXNO-UHFFFAOYSA-N 0.000 description 1
- HLOWSRILNXDHOJ-UHFFFAOYSA-N 2-[6-aminohexyl(2-hydroxyethyl)amino]ethanol Chemical compound NCCCCCCN(CCO)CCO HLOWSRILNXDHOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- QHQUCZUMDKETKO-UHFFFAOYSA-N 3,8-diaminooctyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCC(CCCCCN)N QHQUCZUMDKETKO-UHFFFAOYSA-N 0.000 description 1
- JYFUUUOLQBJAJA-UHFFFAOYSA-N 3-amino-3-(5-aminopentyl)pentane-1,5-diol Chemical compound NCCCCCC(N)(CCO)CCO JYFUUUOLQBJAJA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003327 cancerostatic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PTFDTQDDWWQYMG-UHFFFAOYSA-N methanamine;4-methylbenzenesulfonic acid Chemical compound [NH3+]C.CC1=CC=C(S([O-])(=O)=O)C=C1 PTFDTQDDWWQYMG-UHFFFAOYSA-N 0.000 description 1
- ZUXUNWLVIWKEHB-UHFFFAOYSA-N n',n'-dimethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN ZUXUNWLVIWKEHB-UHFFFAOYSA-N 0.000 description 1
- GWLOGZRVYXAHRE-UHFFFAOYSA-N n,4-dimethylbenzenesulfonamide Chemical compound CNS(=O)(=O)C1=CC=C(C)C=C1 GWLOGZRVYXAHRE-UHFFFAOYSA-N 0.000 description 1
- KYXUJLZIVXPGFZ-UHFFFAOYSA-N n-methylhexan-1-imine Chemical compound CCCCCC=NC KYXUJLZIVXPGFZ-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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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
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/50—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acid amides
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- 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
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/09—Diamines
- C07C211/12—1,6-Diaminohexanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/14—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by amino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/17—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/18—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
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- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- C—CHEMISTRY; METALLURGY
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- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
- C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
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Description
● 窒素原子への単結合(この場合、前駆体は1,6−ヘキサンジアミンである)、
● 酸素原子への単結合(この場合、前駆体は1,6−ヘキサンジオールである)、
● 酸素原子への二重結合(この場合、前駆体はアジポアルデヒドである)、
● 酸素原子への二重結合および酸素原子への単結合(この場合、前駆体はアジピン酸またはアジピン酸ジエステルである)
のいずれかによって結合している、6個の炭素原子の直鎖状配列を有する。
の部分的にN−ヒドロキシエチル化されたtert−1,6−ヘキサンジアミンのファミリーに属する少なくとも1種の窒素化合物の合成方法を提供する。
− N−(2−ヒドロキシエチル)−1,6−ヘキサンジアミン、N,N’−ジ(2−ヒドロキシエチル)−1,6−ヘキサンジアミン、N,N−ジ(2−ヒドロキシエチル)−1,6−ヘキサンジアミンおよびN,N,N’−トリ(2−ヒドロキシエチル)−1,6−ヘキサンジアミンを含むリストから選択される少なくとも1種の中間体化合物を形成する、1,6−ヘキサンジアミンとエチレンオキシドとの間の第1の反応工程と、
− 少なくとも1種の一般式(I)による化合物を形成する、前記少なくとも1種の中間体化合物の第1級または第2級アミン官能基のメチル化を行う第2の工程と
を含む。
− 好ましくは水素および水素化触媒の存在下で、1,6−ヘキサンジオールとメチルアミンとの間で縮合反応させて、N,N’−ジメチル−1,6−ヘキサンジアミンを生成する、第1の工程と、
− N,N’−ジメチル−1,6−ヘキサンジアミンとエチレンオキシドとの間で反応させて、N,N’−ジメチル−N,N’−ジ(2−ヒドロキシエチル)−1,6−ヘキサンジアミンを生成する、第2の反応工程と
を含む。
− アジポアルデヒドとメチルアミンとの間の縮合によって、1,6−ビス(メチルイミノ)−ヘキサンを生成する、第1の反応工程と、
− 1,6−ビス(メチルイミノ)−ヘキサンを還元して、N,N’−ジメチル−1,6−ヘキサンジアミンを生成する、第2の反応工程と、
− エチレンオキシドを用いてN,N’−ジメチル−1,6−ヘキサンジアミンをエトキシ化して、N,N’−ジメチル−N,N’−ジ(2−ヒドロキシエチル)−1,6−ヘキサンジアミンを生成する、第3の反応工程と
を含む。
− N−メチル−2−アミノエタノールとアジピン酸またはアジピン酸ジエステルとを縮合させ、前記アジピン酸ジエステルが好ましくはアジピン酸ジメチルまたはアジピン酸ジエチルであり、それによってN,N’−ジメチル−N,N’−ジ(2−ヒドロキシエチル)−アジポアミドを生成する、第1の反応工程と、
− N,N’−ジメチル−N,N’−ジ(2−ヒドロキシエチル)−アジポアミドのアミド官能基を第3級アミン官能基に還元して、N,N’−ジメチル−N,N’−ジ(2−ヒドロキシエチル)−1,6−ヘキサンジアミンを生成する、第2の工程と
を含む。
− メチルアミンとアジピン酸またはアジピン酸ジエステルとを縮合させ、前記アジピン酸ジエステルが好ましくはアジピン酸ジメチルまたはアジピン酸ジエチルであり、それによってN,N’−ジメチル−N,N’−アジポアミドを生成する、第1の工程と、
− 好ましくは接触水素化によってまたは水素化物、好ましくは水素化リチウムおよびアルミニウムの作用を通して、N,N’−ジメチル−N,N’−アジポアミドのアミド官能基を第3級アミン官能基に還元して、N,N’−ジメチル−1,6−ヘキサンジアミンを生成する、第2の工程と、
− エチレンオキシドを用いてN,N’−ジメチル−1,6−ヘキサンジアミンの第2級アミン官能基をエトキシ化し、N,N’−ジメチル−N,N’−ジ(2−ヒドロキシエチル)−1,6−ヘキサンジアミンを生成する、第3の工程と
を含む。
− 水素触媒の存在下で、1,6−ヘキサンジアミンをホルムアルデヒドおよび水素と反応させることによって部分的にメチル化し、N−メチル−1,6−ヘキサンジアミン、N,N−ジメチル−1,6−ヘキサンジアミン、N,N’−ジメチル−1,6−ヘキサンジアミンおよびN,N,N’−トリメチル−1,6−ヘキサンジアミンを含むリストから選択される少なくとも1種の中間体化合物を生成する、第1の工程と、
− エチレンオキシドと少なくとも1種の中間体化合物とを反応させて、少なくとも1種の一般式(I)の化合物を生成する、第2の反応工程と
を含む。
を有する部分的にN−ヒドロキシエチル化されたtert−1,6−ヘキサンジアミンの合成に関する。
− 以下の式(I1)を有するN,N,N’−トリメチル−N’−(2−ヒドロキシエチル)−1,6−ヘキサンジアミン:
1,6−ヘキサンジアミンからの合成
図1は、式(III)の1,6−ヘキサンジアミンからの少なくとも1種の一般式(I)の化合物の合成を示す。
またはこれらの化合物(式I1〜I4)の組み合わせを第2の工程の最後に得ることができる。
1,6−ヘキサンジオールからの合成
一般式(I)の化合物を、1,6−ヘキサンジオール[式(V)]から合成することができる。
アジポアルデヒドからの合成
一般式(I)の化合物は、アジポアルデヒドから合成することができる。
3段階反応工程における合成
一般式(I)の化合物は、アジポアルデヒド[式(VII)]からの3段階の反応工程において合成することができる。
1段階反応工程における合成
一般式(I)の化合物は、アジポアルデヒド[式(VII)]から一段階反応工程で合成することができる。
アジピン酸からまたはアジピン酸ジエステルからの合成
一般式(I)の化合物は、アジピン酸から、またはアジピン酸ジエステルから合成することができる。
2段階反応工程における合成
一般式(I)の化合物は、アジピン酸[式(XI)]からまたはアジピン酸ジメチル[式(X)]等のアジピン酸ジエステルからの2段階反応工程において合成することができる。
3段階反応工程における合成
一般式(I)の化合物は、アジピン酸[式(XI)]から、またはアジピン酸ジメチル[式(X)]等のアジピン酸ジエステルからの3段階反応工程において合成することができる。
付録: 化合物名および図面中に掲載されるそれらの式の一覧
Claims (7)
- 以下の一般式(I):
を有する、部分的にN−ヒドロキシエチル化されたtert−1,6−ヘキサンジアミンのファミリーに属する少なくとも1種の窒素化合物の合成方法であって、
2個の反応工程を含み、
第1のハロゲン原子非含有前駆体化合物と第2のハロゲン原子非含有前駆体化合物との間の少なくとも第1の反応を含み、
前記2個の反応工程のうちいずれも、ハロゲン化反応物質を含まない、方法であって、
前記第1の前駆体化合物が1,6−ヘキサンジアミンであり、前記第2の前駆体化合物がエチレンオキシドであり、
前記方法が、
N−(2−ヒドロキシエチル)−1,6−ヘキサンジアミン、N,N’−ジ(2−ヒドロキシエチル)−1,6−ヘキサンジアミン、N,N−ジ(2−ヒドロキシエチル)−1,6−ヘキサンジアミンおよびN,N,N’−トリ(2−ヒドロキシエチル)−1,6−ヘキサンジアミンを含むリストから選択される少なくとも1種の中間体化合物を形成する、1,6−ヘキサンジアミンとエチレンオキシドとの間の第1の反応工程と、
少なくとも1種の一般式(I)による化合物を形成する、前記少なくとも1種の中間体化合物の第1級または第2級アミン官能基のメチル化を行う第2の工程とを含み、
前記第2のメチル化工程が、水素化触媒の存在下で前記中間体化合物とホルムアルデヒドと水素との間での反応によって、またはエシュヴァイラー‐クラーク反応に従って前記中間体化合物とホルムアルデヒドとギ酸との間での反応によって行われる、方法。 - 第1の反応工程の終わりに反応していなかった残留1,6−ヘキサンジアミンが、前記少なくとも1種の中間体化合物から前記1,6−ヘキサンジアミンを蒸留することによって分離した後、前記第1の反応工程にリサイクルされる、請求項1または2に記載の方法。
- エチレンオキシドの1,6−ヘキサンジアミンに対するモル比が、3/1以下である、請求項1〜3のいずれか1項に記載の方法。
- エチレンオキシドの1,6−ヘキサンジアミンに対するモル比が、2.5/1以下である、請求項1〜3のいずれか1項に記載の方法。
- 第1の反応工程の終わりに、少なくとも1種の中間体化合物の少なくとも1つの分離工程をさらに含み、それによって第2のメチル化工程の終わりに、一般式(I)に該当する特定の化合物または一般式(I)に該当する特定の化合物の組み合わせを形成する、請求項1〜5のいずれか1項に記載の方法。
- 第1の反応工程の終わりに、少なくとも1種の中間体化合物の蒸留による少なくとも1つの分離工程をさらに含み、それによって第2のメチル化工程の終わりに、一般式(I)に該当する特定の化合物または一般式(I)に該当する特定の化合物の組み合わせを形成する、請求項1〜5のいずれか1項に記載の方法。
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PCT/EP2016/080669 WO2017102659A1 (fr) | 2015-12-17 | 2016-12-12 | Procede ameliore de synthese de 1,6-hexanediamines tertiaires partiellement n-hydroxyethylees |
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