CN115244029A - Process for preparing alkylated amines - Google Patents
Process for preparing alkylated amines Download PDFInfo
- Publication number
- CN115244029A CN115244029A CN202080098306.9A CN202080098306A CN115244029A CN 115244029 A CN115244029 A CN 115244029A CN 202080098306 A CN202080098306 A CN 202080098306A CN 115244029 A CN115244029 A CN 115244029A
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- CN
- China
- Prior art keywords
- amine
- tris
- hydrogen
- solution
- primary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000001412 amines Chemical class 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 20
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- -1 octylenediamine Chemical compound 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007983 Tris buffer Substances 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 15
- 150000003141 primary amines Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 4
- QMXSDTGNCZVWTB-UHFFFAOYSA-N n',n'-bis(3-aminopropyl)propane-1,3-diamine Chemical compound NCCCN(CCCN)CCCN QMXSDTGNCZVWTB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 3
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 2
- XIDCCVQQSRGENZ-UHFFFAOYSA-N methanetetramine Chemical compound NC(N)(N)N XIDCCVQQSRGENZ-UHFFFAOYSA-N 0.000 claims description 2
- BKHGFBHADSLTHZ-UHFFFAOYSA-N n',n'-bis(4-aminobutyl)butane-1,4-diamine Chemical compound NCCCCN(CCCCN)CCCCN BKHGFBHADSLTHZ-UHFFFAOYSA-N 0.000 claims description 2
- JNZCEYWMODDEQC-UHFFFAOYSA-N n',n'-bis(5-aminopentyl)pentane-1,5-diamine Chemical compound NCCCCCN(CCCCCN)CCCCCN JNZCEYWMODDEQC-UHFFFAOYSA-N 0.000 claims description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 142
- 229910052757 nitrogen Inorganic materials 0.000 description 110
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 94
- 239000000243 solution Substances 0.000 description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 66
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 55
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 49
- 239000008367 deionised water Substances 0.000 description 40
- 229910021641 deionized water Inorganic materials 0.000 description 40
- 238000003756 stirring Methods 0.000 description 38
- 239000010453 quartz Substances 0.000 description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- 239000002243 precursor Substances 0.000 description 36
- 229910010413 TiO 2 Inorganic materials 0.000 description 28
- 239000004305 biphenyl Substances 0.000 description 27
- 235000010290 biphenyl Nutrition 0.000 description 27
- 238000002256 photodeposition Methods 0.000 description 25
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 101150003085 Pdcl gene Proteins 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- 238000005119 centrifugation Methods 0.000 description 22
- 238000005303 weighing Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 18
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000011941 photocatalyst Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000003517 fume Substances 0.000 description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- 230000003134 recirculating effect Effects 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 12
- 230000007935 neutral effect Effects 0.000 description 10
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 9
- 238000001139 pH measurement Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000006755 (C2-C20) alkyl group Chemical group 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- 229910002710 Au-Pd Inorganic materials 0.000 description 1
- 229910025794 LaB6 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- 229910018885 Pt—Au Inorganic materials 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- URKRYOHZWVRTIL-UHFFFAOYSA-N n',n'-bis[2-(diethylamino)ethyl]-n,n-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CCN(CC)CC)CCN(CC)CC URKRYOHZWVRTIL-UHFFFAOYSA-N 0.000 description 1
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 description 1
- DTKANQSCBACEPK-UHFFFAOYSA-N n',n'-bis[3-(dimethylamino)propyl]-n,n-dimethylpropane-1,3-diamine Chemical compound CN(C)CCCN(CCCN(C)C)CCCN(C)C DTKANQSCBACEPK-UHFFFAOYSA-N 0.000 description 1
- LSICDRUYCNGRIF-UHFFFAOYSA-N n,n-dimethylheptan-1-amine Chemical compound CCCCCCCN(C)C LSICDRUYCNGRIF-UHFFFAOYSA-N 0.000 description 1
- QMHNQZGXPNCMCO-UHFFFAOYSA-N n,n-dimethylhexan-1-amine Chemical compound CCCCCCN(C)C QMHNQZGXPNCMCO-UHFFFAOYSA-N 0.000 description 1
- AMAADDMFZSZCNT-UHFFFAOYSA-N n,n-dimethylnonan-1-amine Chemical compound CCCCCCCCCN(C)C AMAADDMFZSZCNT-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- IDFANOPDMXWIOP-UHFFFAOYSA-N n,n-dimethylpentan-1-amine Chemical compound CCCCCN(C)C IDFANOPDMXWIOP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006485 reductive methylation reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- BSYLOTSXNQZYFW-UHFFFAOYSA-K trichlorogold;hydrate Chemical compound O.Cl[Au](Cl)Cl BSYLOTSXNQZYFW-UHFFFAOYSA-K 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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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Abstract
The present invention relates to a process for producing an alkylated amine by reacting a primary or secondary amine with an alcohol in the presence of hydrogen, a metal catalyst supported by a photosensitive titanium oxide, and UV irradiation. Advantageously, the reaction can be carried out under mild reaction conditions.
Description
Technical Field
The present invention relates to a process for the preparation of alkylated amines.
Background
N, N, N', N "-Pentamethyldiethylenetriamine (PMDTA) is used in the formation of rigid foam polyurethane. Current PMDTA production technology relies on the methylation of Diethylenetriamine (DETA) in the presence of hydrogen by using formaldehyde as a methyl source. This method is selective for PMDTA. However, the use of formaldehyde (CMR compound) causes HSE problems.
For example, U.S. patent No. 5105013 teaches a method for preparing permethylated amines, particularly pentamethyldiethylenetriamine, by reductive methylation of diethylenetriamine in the presence of hydrogen, aqueous formaldehyde, a catalyst and a solvent. The reaction is carried out in two reaction stages and the flow rate of formaldehyde must be well controlled.
RSC Adv [ RSC evolution]2015,5,14514-14521 report the preparation of a series of TiO 2 Supported nano-Pd catalyst (Pd/TiO) 2 ) And used for N, N-dimethylation of different amines and nitro compounds with methanol under UV irradiation at room temperature. The working atmosphere was argon.
There are several well known processes for alkylating amines using alcohols as alkylating agents in the presence of hydrogen and a catalyst other than a photocatalyst. For example, baiker _ et al Helvetica Chimica Acta [ Switzerland Chemicals ] volume 61, vol.3 (1978), vol.112, 1169-1174 and T.Yamakawa et al Catalysis Communications [ catalytic Communications ]5 (2004) 291-295 disclose the use of heterogeneous metal catalysts, particularly copper-based catalysts. ACS susteable chem. Eng. [ Sustainable chemical and engineering by the american chemical society ]2019,7,1,716-723 reports the use of homogeneous ruthenium-based catalysts. However, all reactions require hydrogen at high temperature and pressure.
Accordingly, there remains a need to develop an environmentally friendly process for alkylating amines under mild reaction conditions with high yield and selectivity that can overcome the disadvantages of the prior art.
Disclosure of Invention
The present invention therefore relates to a process for preparing alkylated amines by reacting a primary or secondary amine with an alcohol in the presence of hydrogen, a metal catalyst supported by a photosensitive titanium oxide and UV irradiation.
The process of the present invention enables the alkylation of amines in higher yields by using environmentally friendly alkylating agents.
Advantageously, the reaction according to the invention can be carried out at low hydrogen pressure and low reaction temperature.
The invention also relates to a mixture comprising:
(i) A primary or secondary amine, or a mixture thereof,
(ii) An alcohol in the form of a mixture of alcohols,
(iii) Hydrogen gas, and
(iv) A metal catalyst supported by a photosensitive titanium oxide.
Other objects and features, aspects and advantages of the present invention will become more apparent upon reading the following detailed description and examples.
Drawings
FIG. 1 is H from the reaction of octylamine with methanol in example 8 2 Image of pressure-yield curve.
Definition of
Throughout this specification, including the claims, unless otherwise indicated, the terms "comprising a" and "an" should be understood as being synonymous with the terms "comprising at least one" and "between 8230the" should be understood as including the extremes.
As used herein, the term "organic radical" (C) n -C m ) "(wherein n and m are both integers) indicates that the group may contain from n carbon atoms to m carbon atoms per group.
The use of the articles "a" and "the" means that the grammatical object of the article is a member or members of a group (i.e., at least one).
The term "and/or" includes the meaning of "and", "or" and also includes all other possible combinations of elements connected to the term.
It should be noted that for continuity of description, the limits are included within the range of values given unless otherwise indicated.
Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value or sub-range is explicitly recited.
Detailed Description
In some embodiments, the primary or secondary amine used in the process according to the invention may have the general formula (I):
R 1 R 2 NH (I)
R 1 and R 2 Independently of one another, may represent hydrogen, or a linear, branched or cyclic hydrocarbon radical, optionally interrupted by one or several heteroatoms and/or optionally substituted by one or several functional groups. R 1 And R 2 Not all are hydrogen at the same time. The heteroatom may be O, S, F, or N.
R 1 And R 2 Independently of one another, may represent hydrogen, alkyl, alkenyl, aryl, cycloalkyl or heterocyclic groups.
R 1 And R 2 Independently of one another, may be especially hydrogen, C 2 -C 20 Alkyl, alkenyl, aryl or heterocyclic group, and preferably hydrogen, C 3 -C 10 An alkyl, alkenyl, aryl, or heterocyclic group.
Advantageously, R 1 Is hydrogen and R 2 Is an alkyl group selected from the group consisting of: ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl.
In some embodiments, the primary or secondary amines according to the invention may have the general formula (II):
wherein:
-n is an integer between 0 and 20;
-m is an integer between 1 and 3;
-p is an integer between 0 and 2, and
-p+m＝3。
in a preferred embodiment, the compound having the general formula (II) is a compound having the general formula (III):
wherein n is an integer between 0 and 20, preferably between 0 and 9 and more preferably between 0 and 4.
In another preferred embodiment, the compound having the general formula (II) is a compound having the general formula (IV):
wherein n is an integer between 0 and 20, preferably between 0 and 9 and more preferably between 0 and 4.
In a third preferred embodiment, the compound having general formula (II) is a compound having general formula (V):
wherein n is an integer between 0 and 20, preferably between 0 and 9 and more preferably between 0 and 4.
The compound having the general formula (II) may be selected from the group consisting of: dimethylenetriamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, dihexylylenetriamine, diheptylenetriamine, dioctylenetriamine, dinonylenetriamine, didecylenetriamine, methylenediamine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine and decyylenediamine, triaminomethylamine, tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, tris (4-aminobutyl) amine, tris (5-aminopentyl) amine, tris (6-aminohexyl) amine, tris (7-aminoheptyl) amine, tris (8-aminooctyl) amine, tris (9-aminononyl) amine and tris (10-aminodecyl) amine.
Preferably, the compound having the general formula (II) may be selected from the group consisting of: diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, ethylenediamine, propylenediamine, butylenediamine, and pentylenediamine.
The alcohol used in the process according to the invention may have the general formula (VI):
R 3 OH (VI)
wherein R is 3 Is alkyl, alkenyl or alkynyl.
Preferably, R 3 And may be straight chain or branched. More preferably, R 3 May be C 1 -C 10 Linear or branched alkyl.
Examples of alcohols having the general formula (VI) are methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 2-propanol, 2-butanol and 3-butanol.
Preferably, the alcohol having general formula (VI) may be selected from the group consisting of: methanol, ethanol, 1-propanol and 2-propanol.
The alcohol may contain minor amounts of the corresponding aldehyde and/or carboxylic acid. For example, methanol may contain traces of formaldehyde and/or formic acid, ethanol may contain traces of acetaldehyde and/or acetic acid, and propanol may contain traces of propionaldehyde and/or propionic acid. Advantageously, the alcohol may comprise from 0.01 to 10000ppm of the corresponding aldehyde and/or carboxylic acid.
It will be appreciated by the skilled person that primary or secondary amines may be partially or fully alkylated by the process according to the invention.
The preferred reaction of the present invention is as follows:
R 3 n, m and p have the meanings defined aboveThe same meaning is used.
R 1 And R 3 Have the same meaning as defined above.
Examples of preferred reactions are as follows:
-pentylamine is reacted with methanol to produce dimethylpentylamine;
-hexylamine is reacted with methanol to produce dimethylhexylamine;
-heptylamine reacts with methanol to produce dimethylheptylamine;
-octylamine is reacted with methanol to produce dimethyloctylamine;
-reacting nonyl amine with methanol to produce dimethyl nonyl amine;
-diethylenetriamine reacting with methanol to produce N, N', N "-pentamethyldiethylenetriamine;
-reacting diethylenetriamine with ethanol to produce N, N', N "-pentaethyldiethylenetriamine;
-reacting diethylenetriamine with 1-propanol to produce N, N', N "-pentapropyl diethylenetriamine;
-reacting diethylenetriamine with 2-propanol to produce N, N', N "-pentaisopropyl diethylenetriamine;
-dipropylenetriamine with methanol to produce N, N', N "-pentamethyldipropylenetriamine;
-dipropylenetriamine with ethanol to produce N, N', N "-pentaethyldipropylenetriamine;
-dipropylenetriamine with 1-propanol to produce N, N', N "-pentapropyl dipropylenetriamine;
-dipropylenetriamine with 2-propanol to give N, N', N "-pentaisopropyldipropylenetriamine;
-reacting ethylenediamine with methanol to produce N, N' -tetramethylethane-1, 2-diamine;
-ethylenediamine reacts with ethanol to produce N, N' -tetraethylethane-1, 2-diamine;
-reacting ethylenediamine with 1-propanol to give N, N' -tetrapropylethane-1, 2-diamine;
-ethylenediamine with 2-propanol to give N, N' -tetraisopropylethane-1, 2-diamine;
-propylenediamine reacts with methanol to produce N, N' -tetramethylpropane-1, 3-diamine;
-propylenediamine reacts with ethanol to produce N, N' -tetraethylpropane-1, 3-diamine;
-propylenediamine is reacted with 1-propanol to give N, N' -tetrapropylpropane-1, 3-diamine;
-propylenediamine is reacted with 2-propanol to give N, N' -tetraisopropylpropane-1, 3-diamine;
-tris (2-aminoethyl) amine with methanol to to produce tris [2- (dimethylamino) ethyl ] amine;
-reacting tris (2-aminoethyl) amine with ethanol to produce tris [2- (diethylamino) ethyl ] amine;
-tris (2-aminoethyl) amine is reacted with 1-propanol to produce tris [2- (di-n-propylamino) ethyl ] amine;
-tris (2-aminoethyl) amine is reacted with 2-propanol to produce tris [2- (di-isopropylamino) ethyl ] amine.
-reacting tris (3-aminopropyl) amine with methanol to produce tris [3- (dimethylamino) propyl ] amine;
-reacting tris (3-aminopropyl) amine with ethanol to produce tris [3- (diethylamino) propyl ] amine;
-tris (3-aminopropyl) amine is reacted with 1-propanol to produce tris [3- (di-n-propylamino) propyl ] amine;
-tris (3-aminopropyl) amine is reacted with 2-propanol to produce tris [3- (di-isopropylamino) propyl ] amine.
The metal supported on the photosensitive titanium oxide is not particularly limited. Advantageously, the metal is a noble metal. Precious metals are metals that are generally valuable and resistant to corrosion and oxidation in humid air. It may be selected from the group consisting of: ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold. Of these noble metals, palladium, gold, platinum and silver are preferred and palladium is more preferred.
In some embodiments, one and only one noble metal is supported on the photosensitive titanium oxide. In this embodiment, the loading amount of the noble metal on the photosensitive titanium oxide may be in the range of 0.01 to 10wt%, preferably 0.01 to 2wt%, and more preferably 0.01 to 1.5 wt%.
In some embodiments, at least two metals are supported on the photosensitive titanium oxide. The two metals may be any combination of palladium, gold, platinum, silver, copper and molybdenum. In this example, the loading of each metal on the photosensitive titanium oxide depends on the particular metal. Advantageously, at least Pt-Au, pd-Au or Pt-Pd is supported on the photosensitive titanium oxide. The supported amount of Pd, pt, or Au on the photosensitive titanium oxide may be in the range of 0.01 to 10wt%, preferably 0.01 to 2wt%, and more preferably 0.01 to 1.5 wt%.
The average primary particle size of the metal nanoparticles on the photosensitive titanium oxide is from 0.5 to 40nm and preferably from 1 to 20nm, which is measured using a Transmission Electron Microscope (TEM).
For TEM analysis, JEOL 2100 with file LaB6 with an acceleration voltage of 200kV equipped with a camera Gatan 832CCD was used. As a support, a square 230-mesh TEM support grid (copper) was used. The magnification has a range of '10,000 to' 600,000. For 50nm: a magnification of 40,000 to 50,000; for a 20nm:60,000 to 120,000; for 10nm:250,000; for 5nm:400,000; for 2nm:500,000 to 600,000. Measurements were made on a sample of 0.1wt% nanoparticles in methanol suspension. The results obtained were analyzed using digital micrograph software. For each sample, two photographs were taken and a total of 100 nanoparticles were analyzed to obtain the size distribution. From this size distribution, the average particle size of the nanoparticles is obtained. The software used to measure the size of the nanoparticles was ImageJ, approximating the particles as spheres. After setting the ratio, the maximum diameter of the particles was manually measured one after another until the total number of measured particles was 100. Each particle was measured 3 times to obtain the average size.
Photosensitive titanium oxide (TiO) 2 ) Also known as titanium dioxide, there are three known crystal forms, rutile, anatase and brookite. Anatase and rutile are preferred crystal forms according to the present invention. In a preferred embodiment, the photosensitive titanium oxide is a mixture of anatase and rutile crystals.
The BET surface area of the crystals of the photosensitive titanium oxide may preferably be from 10 to 600m 2 G and preferably from 30 to 400m 2 /g。
The term "specific surface area" is understood to mean The BET specific surface area determined by nitrogen adsorption according to The standard ASTM D3663-78 established by The Brunauer-Emmett-Teller method described in The Journal of The American Chemical Society, 60,309 (1938).
In a preferred embodiment, the photosensitive titanium oxide is in the anatase crystalline form and has a particle size of between 70 and 120m 2 Per g and preferably from 80 to 100m 2 BET surface area in the range of/g. An example of such a photosensitive titanium oxide is PC105 from Cristal corporation.
In another embodiment, the photosensitive titanium oxide is in the anatase crystalline form and has a particle size of between 300 and 400m 2 G and preferably 330 to 370m 2 BET surface area in the range/g. An example of such a photosensitive titanium oxide is PC500 from Cristal corporation.
In a third embodiment, the photosensitive titanium oxide is a mixture of anatase and rutile crystals, wherein the anatase content is 80-90% by weight and the rutile content is 10-20% by weight. In this embodiment, the photosensitive titanium oxide may have a thickness of 20 to 80m 2 Per g and preferably from 35 to 65m 2 BET surface area in the range/g. An example of such a photosensitive titanium oxide is P25 from winning inc (Evonik). In this embodiment, the photosensitive titanium oxide may also have a thickness of 50 to 130m 2 G and preferably from 70 to 110m 2 BET surface area in the range of/g. An example of such a photosensitive titanium oxide is P90 from the winning company.
Advantageously, the photosensitive titanium oxide used in the method according to the invention is P25 or P90, and preferably P90.
Some typical ultraviolet light devices, such as xenon lamps or LED lamps, can achieve UV radiation. Preferably, the irradiation power of the UV light may be from 1 to 320W, preferably from 8 to 310W.
The supported metal catalysts according to the invention can be obtained by various known methods. For example, the precipitation-reduction method: RSC Adv [ RSC evolution ],2015,5,14514-14521 and photo-deposition: chem. [ journal of organic chemistry ]2017,82,5959-5965.
Advantageously, the supported metal catalyst is prepared by a photo-deposition process. In a typical process, it may comprise the steps of:
a) An aqueous solution of a metal precursor is prepared,
b) Mixing the photosensitive titanium oxide with the solution prepared in step a),
c) Stirring the mixture obtained in step b) at room temperature for a suitable time in an inert atmosphere in the absence of light irradiation,
d) Stirring the mixture obtained in step c) at room temperature under inert atmosphere and UV irradiation for a suitable time,
e) Centrifuging the mixture obtained in step d) to obtain a solid product,
f) Washing the solid product obtained in step e) with a solvent until the pH becomes neutral,
g) Drying the solid product obtained in step f).
Preferably, the concentration of the metal precursor in step a) may be in the range of 0.0005 to 0.50mol/L and preferably from 0.001 to 0.05 mol/L.
Preferably, the irradiation power of the UV light in step d) may be from 1 to 320W, preferably from 8 to 310W.
Preferably, the solvent in step f) may be water and preferably deionized water.
The weight ratio of supported metal catalyst to primary or secondary amine is from 0.001 to 100 and preferably from 0.01 to 10.
The weight ratio of primary or secondary amine to alcohol can be from 0.0001 to 0.5 and preferably from 0.001 to 0.2.
According to the process of the present invention, in a preferred embodiment, the alcohol is the reactant and is also the sole solvent for the primary or secondary amine. The skilled person will appreciate that the reaction may also be carried out in the presence of a second solvent other than an alcohol, provided that the second solvent does not participate in the reaction in place of the alcohol. Examples of such solvents are water, formaldehyde (trace), formic acid (trace), benzene, toluene, dimethyl ether, and the like.
The concentration of the primary or secondary amine in the solvent may be from 0.01 to 50wt% and preferably from 0.1 to 20wt%.
Although not particularly limited, the reaction of the primary or secondary amine with the alcohol is desirably carried out under a hydrogen pressure in the range of 0.1 to 20 bar, and more preferably 0.5 to 12 bar. Optionally, hydrogen may be added during the reaction to make up for consumption or to continuously circulate throughout the reaction zone.
The reaction may be carried out under an inert atmosphere such as N 2 Or in the presence of Ar.
The reaction time may be from 0.5 to 100h and preferably from 2 to 60h.
The reaction temperature may be from 0 ℃ to 100 ℃, and preferably from 10 ℃ to 50 ℃ and more preferably room temperature.
The invention also relates to a mixture comprising:
(i) A primary or secondary amine, or a mixture thereof,
(ii) An alcohol in the form of a mixture of alcohols,
(iii) Hydrogen gas, and
(iv) A metal catalyst supported by a photosensitive titanium oxide.
The mixture may further comprise a second solvent selected from the group consisting of: water, formaldehyde, formic acid, benzene, toluene and dimethyl ether.
The mixture may further comprise an alkylated amine prepared by the process of the invention.
The primary or secondary amine, alcohol and metal catalyst have the same meaning as defined above.
Examples of the invention
The technical features and technical effects of the present invention will be further described below in conjunction with the following examples so that those skilled in the art will fully understand the present invention. Those skilled in the art will readily appreciate that the examples herein are for illustrative purposes only and that the scope of the present invention is not limited thereto.
Material
-
TiO 2 P25, CAS number 13463-67-7, 99.5%, winning group
-
TiO 2 P90, CAS number 13463-67-7, 99.5%, winning group
-CristalACTIV TM PC105, CAS number 13463-67-7, cristal ACTIV Inc
-CristalACTIV TM PC500, CAS number 13463-67-7, cristal ACTIV Inc
Gold (III) chloride hydrate, CAS number 27988-77-8, 99.995%, sigma-Aldrich (Sigma-aldrich)
Silver nitrate, CAS No. 7761-88-8, analytical grade (AR), national pharmaceutical group (Sino Pharm)
Palladium chloride, CAS No. 7647-10-1, 99.5%, sigma-Aldrich
Hydrochloric acid, CAS number 7647-01-0, 36.0% -38.0%, pharmaceutical group
Sodium hydroxide, CAS No. 1310-73-2, analytical pure, national pharmaceutical group
Sodium borohydride, CAS number 16940-66-2, 96%, pharmaceutical group
Octylamine, CAS No. 111-86-4, 99%, J & K Corp
Biphenyl, CAS number 92-52-4, 99.5%, J & K Corp
Methanol, CAS number 67-56-1, 99.9%, merck
Isopropanol, CAS number 67-63-0, 99.9%, merck
Diethylenetriamine, CAS number 111-40-0, 99%, sigma-Aldrich
Pentamethyldiethylenetriamine, CAS No. 3030-47-5, 99%, sigma-aldrich.
Preparation of the monometallic catalyst by deposition-precipitation-reduction:
Pd/TiO 2 (FJ-056-342)
weighing a mass of TiO 2 (P90, 1.9840 g) and added to a round bottom flask followed by a volume of deionized water (140 mL).
Weighing a mass of a metal precursor H 2 PdCl 4 (H 2 PdCl 4 0.025g/mL in dilute aqueous HCl -1 ，1.51mL)。(H 2 PdCl 4 In dilute aqueous HCl by reacting PdCl 2 (0.1769 g) dissolved in 37% (v/v) HCl (0.53 mL) and water added to dilute the solution to 10mL prepared, chemSusChem [ chemical and sustainability, energy and materials ]]2013,6,1923-1930。)
Adding an aqueous solution of a metal precursor to a solution containing TiO 2 And deionized water, and the solution was stirred vigorously at room temperature for several hours.
A1 mol/L NaOH solution was prepared beforehand with deionized water. The sodium hydroxide solution was added dropwise to the previous reaction flask with stirring in order to adjust the pH to 10 (pH measured by a calibrated pH meter), and then the solution was stirred vigorously at room temperature for several hours.
Weigh a mass of NaBH in a beaker 4 Solid (0.1138 g) and dissolved in deionized water (15 mL). The sodium borohydride solution was then added to a round bottom flask that was settled in an ice bath (at 0 ℃) and the resulting solution was stirred vigorously for several hours at 0 ℃. A grey (for Pd) milky solution was obtained.
The solution was transferred from the round bottom flask to a centrifuge tube for centrifugation (15000 rpm). The product was treated by repeating the deionized water addition, centrifugation, wastewater decanting and pH measurement until the pH became neutral (equal to 7).
The resulting catalyst was transferred to a clean round bottom flask, heated at 80 ℃ and evaporated by vacuum using a pump to dry the deionized water, and the dried catalyst was analyzed by TEM, ICP, UV-Vis spectroscopy (if needed) and stored in a sample bottle under argon.
Au/TiO 2 (FJ-056-368)
Weighing a mass of metal precursor AuCl 3 ·xH 2 O (Au 49wt% in AuCl) 3 ·xH 2 O, 0.0165 g) and added to the round bottom flask.
Weighing a mass of TiO 2 (P90, 0.9924 g) and a volume of deionized water (70 mL) were added to the round bottom flask.
Adding an aqueous solution of a metal precursor to a solution containing TiO 2 And deionized water, and the solution was stirred vigorously at room temperature for several hours.
A1 mol/L NaOH solution was prepared beforehand with deionized water. The sodium hydroxide solution was added dropwise to the previous reaction flask with stirring in order to adjust the pH to 10 (pH measured by a calibrated pH meter), and then the solution was stirred vigorously at room temperature for several hours.
Weigh a mass of NaBH in a beaker 4 Solid (0.0307 g) and dissolved in deionized water (4 mL). The sodium borohydride solution was then added to a round bottom flask that was settled in an ice bath (at 0 ℃) and the resulting solution was stirred vigorously for several hours at 0 ℃. A purple milky solution was obtained.
The solution was transferred from the round bottom flask to a centrifuge tube for centrifugation (15000 rpm). The product was treated by repeating the deionized water addition, centrifugation, wastewater discharge and pH measurement until the pH became neutral (equal to 7).
The resulting catalyst was transferred to a clean round bottom flask, heated at 80 ℃ and evaporated by vacuum using a pump to dry the deionized water and the dried catalyst was analyzed by TEM, ICP, UV-Vis spectroscopy (if needed) and stored in a sample bottle under argon.
Ag/TiO 2 (FJ-056-369)
Weighing a mass of TiO 2 (P90, 0.9939 g) and added to a round bottom flask, followed by a volume of deionized water (70 mL).
Weighing a mass of a metal precursor AgNO 3 (0.0126 g) and added to this round bottom flask. The solution was vigorously stirred at room temperatureStirring was carried out for several hours.
A1 mol/L NaOH solution was prepared beforehand with deionized water. The sodium hydroxide solution was added dropwise to the previous reaction flask with stirring in order to adjust the pH to 10 (pH measured by a calibrated pH meter), and then the solution was stirred vigorously at room temperature for several hours.
Weighing a mass of NaBH in a beaker 4 Solid (0.0565 g) and dissolved in deionized water (7 mL). The sodium borohydride solution was then added to a round bottom flask that was settled in an ice bath (at 0 ℃) and the resulting solution was stirred vigorously for several hours at 0 ℃. A light pink milky solution was obtained.
The solution was transferred from the round bottom flask to a centrifuge tube for centrifugation (15000 rpm). The product was treated by repeating the deionized water addition, centrifugation, wastewater decanting and pH measurement until the pH became neutral (equal to 7).
The resulting catalyst was transferred to a clean round bottom flask, heated at 80 ℃ and evaporated by vacuum using a pump to dry the deionized water and the dried catalyst was analyzed by TEM, ICP, UV-Vis spectroscopy (if needed) and stored in a sample bottle under argon.
Preparation of the monometallic catalyst by photo-deposition:
Pd/TiO 2 (FJ-056-371)
weighing a mass of TiO 2 (P90, 0.4964 g) and added to a Schlenk flask (Schlenk flash) under nitrogen, followed by a volume of deionized water (3.5 mL), followed by isopropanol (4.5 mL).
Weighing a mass of a metal precursor H 2 PdCl 4 (H 2 PdCl 4 0.025g/mL in dilute aqueous HCl -1 0.38 mL) and then dissolved in deionized water, and a precursor solution was prepared. (H) 2 PdCl 4 Is prepared by mixing PdCl 2 (0.1769 g) was dissolved in 37% (v/v) HCl (0.53 mL), and water was added to dilute the solution to 10 mL. )
H is to be 2 PdCl 4 Addition of an aqueous solution of the precursor to the TiO-containing precursor 2 And solvent, and solution (H in the final reaction solution) 2 PdCl 4 The concentration of the precursor was 0.0107 mol/L) was protected with aluminium foil to avoid any light irradiation and was first placed in a microwave for 30 minutes and then stirred vigorously at room temperature for 50 minutes.
The solution was then stirred vigorously under UV (365nm, 22A, 308W) irradiation at room temperature for 1 hour to give a dark gray milky solution.
The solution in the schlank flask was then transferred to a centrifuge tube for centrifugation (15000 rpm). The product was treated by repeating the deionized water addition, centrifugation, waste liquid discharge and pH measurement until the pH became neutral (equal to 7). This procedure was repeated a total of 20 times.
The resulting catalyst was transferred to a clean round bottom flask, heated at 80 ℃ and evaporated by vacuum using a pump to dry the deionized water, and the dried catalyst was analyzed by TEM, ICP, UV-Vis spectroscopy (if needed) and stored in a sample bottle under argon.
AP-056-370 was prepared in the same manner except for the precursor PdNO 3 -xH 2 O, and just 5 minutes of microwave treatment and no previous agitation was initiated prior to UV irradiation.
AP-056-372 was prepared in the same manner except that the current for UV during photo-deposition was 13A,182W.
AP-056-373 was prepared in the same manner except that the current of UV during photo-deposition was 13A,182W, additional volumes of deionized water (14 mL), isopropanol (18 mL) were added and H in the final reaction solution 2 PdCl 4 The concentration of the precursor was 0.0027mol/L and the duration of UV irradiation was 1.5 hours.
AP-056-432 was prepared in the same manner except that the current of UV during photo-deposition was 13A,182W and the catalyst was washed 20 times with isopropanol each time before centrifugation.
AP-056-433 was prepared in the same manner except that the current of UV during photo-deposition was 13A,182W, and the catalyst was washed 3 times with deionized water after centrifugation.
AP-056-459 was prepared in the same manner except that the current of UV was 13A,182W during photo-deposition, and the catalyst was washed 10 times with deionized water after centrifugation.
AP-056-435, AP-056-436, AP-056-456 were prepared in the same manner except that the current of UV during photo-deposition was 13A,182W, pd loading varied; and the duration of UV irradiation of AP-056-436 was 2 hours.
AP-056-488 was prepared in the same manner except that the current of UV during photo-deposition was 13a,182w, the scale of the reaction was 4 times larger, the solution protected with aluminum foil was vigorously stirred at room temperature for 4 hours, and then irradiated with UV for 3 hours with stirring.
AP-056-491 and AP-056-493 were prepared in the same manner except that the current of UV was 13A,182W during photo-deposition, the support was different, and the solution protected with aluminum foil was vigorously stirred at room temperature for 1.5 hours, and then irradiated with UV under stirring for 2 hours.
Au/TiO 2 (FJ-056-381)
Weighing a mass of TiO 2 (P90, 0.4965 g) and added to a Schlenk flask (Schlenk flash) under nitrogen, followed by a volume of deionized water (3.5 mL), followed by isopropanol (4.5 mL).
Weighing a mass of a metal precursor, auCl 3 ·xH 2 O (Au 49wt% in AuCl) 3 ·xH 2 O, 0.0084 g) and added to the solution containing TiO 2 And the solution was protected with aluminum foil to avoid any light irradiation, and it was vigorously stirred at room temperature for 1 hour.
The solution was then stirred vigorously at room temperature for 1 hour under UV (365nm, 13A, 182W) irradiation to give a purple milky solution.
The solution in the schlank flask was then transferred to a centrifuge tube for centrifugation (15000 rpm). The product was treated by repeating the deionized water addition, centrifugation, waste liquid decanting and pH measurement until the pH became neutral (equal to 7).
The resulting catalyst was transferred to a clean round bottom flask, heated at 80 ℃ and evaporated by vacuum using a pump to dry the deionized water and the dried catalyst was analyzed by TEM, ICP, UV-Vis spectroscopy (if needed) and stored in a sample bottle under argon.
Ag/TiO 2 (FJ-056-376)
Weighing a mass of TiO 2 (P90, 0.4965 g) and added to a Schlenk flask (Schlenk flash) under nitrogen, followed by a volume of deionized water (3.5 mL), isopropanol (4.5 mL).
Weighing a mass of a metal precursor AgNO 3 (0.0075 g) and added to a solution containing TiO 2 And the solution was protected with aluminum foil to avoid any light irradiation, and it was vigorously stirred at room temperature for 105 minutes.
This solution was then stirred vigorously under UV (365nm, 13A, 182W) irradiation at room temperature for 1 hour to give a deep yellow to orange milky solution.
The solution in the schlank flask was then transferred to a centrifuge tube for centrifugation (15000 rpm). The product was treated by repeating the deionized water addition, centrifugation, waste liquid decanting and pH measurement until the pH became neutral (equal to 7).
The resulting catalyst was transferred to a clean round bottom flask, heated at 80 ℃ and evaporated by vacuum using a pump to dry the deionized water and the dried catalyst was analyzed by TEM, ICP, UV-Vis spectroscopy (if needed) and stored in a sample bottle under argon.
Preparation of bimetallic catalyst by photo-deposition:
Au-Pd/TiO 2 (FJ-056-458)
weighing a mass of TiO 2 (P90, 0.9834 g) and added to a Schlenk flask under nitrogen atmosphere.
Weighing of metal precursor AuCl 3 ·xH 2 O (Au 49wt% in AuCl) 3 ·xH 2 O, 0.01632 g) and dissolved in deionized water (7.0 mL) and isopropanol (9.0 mL) and a precursor solution was prepared.
The metal precursor solution is then added to the solution containing TiO 2 And the solution was protected with aluminum foil to avoid any light irradiation, and it was vigorously stirred at room temperature for 2 hours.
This solution was then stirred vigorously under UV (365nm, 13A, 182W) irradiation at room temperature for 3 hours until a purple milky solution was obtained. The UV irradiation was then turned off.
Under nitrogen atmosphere, H is then weighed 2 PdCl 4 Precursor (H) 2 PdCl 4 Precursor in dilute aqueous HCl, 0.025g/mL -1 0.75 mL) and dissolved in the previous solution and the solution was protected with aluminum foil to avoid any light irradiation and stirred vigorously at room temperature for 2 hours; then stirred vigorously under UV (365nm, 13A, 182W) irradiation at room temperature for 3 hours until a purple-gray milky solution is obtained. (H) 2 PdCl 4 The precursor is prepared by reacting PdCl 2 (0.1769 g) was dissolved in 37% (v/v) HCl (0.53 mL), and water was added to dilute the solution to 10 mL.
The solution in the schlank flask was then transferred to a centrifuge tube for centrifugation (15000 rpm). The product was treated by repeating the deionized water or isopropanol addition, centrifugation, spent liquor discharge and pH measurement until the pH became neutral (equal to 7). The catalyst was then transferred again to a schlenk flask at room temperature under nitrogen.
Another metal precursor was then added by the procedure described above.
The resulting catalyst was transferred to a clean round bottom flask, heated at 80 ℃ and evaporated by vacuum using a pump to dry the deionized water and the dried catalyst was analyzed by TEM, ICP, UV-Vis spectroscopy (if needed) and stored in a sample bottle under argon.
Pd-Au/TiO 2 (FJ-056-471)
Weighing a mass of TiO 2 (P90, 0.9834 g) and added to a Schlenk flask under nitrogen atmosphere.
Weighing of the Metal precursor H 2 PdCl 4 (H 2 PdCl 4 Precursor in dilute aqueous HCl, 0.025g/mL -1 0.75 mL) and dissolved in deionized water (7.0 mL) and isopropanol (9.0 mL). (H) 2 PdCl 4 The precursor is prepared by reacting PdCl 2 (0.1769 g) was dissolved in 37% (v/v) HCl (0.53 mL), and water was added to dilute the solution to 10 mL.
The metal precursor solution is then added to the solution containing TiO 2 And the solution was protected with aluminum foil to avoid any light irradiation, and it was vigorously stirred at room temperature for 2 hours.
This solution was then stirred vigorously under UV (365nm, 13A, 182W) irradiation at room temperature for 3 hours until a gray milky solution was obtained. The UV irradiation was then turned off.
Under nitrogen atmosphere, the metal precursor AuCl is then weighed 3 ·xH 2 O (Au 49wt% in AuCl) 3 ·xH 2 O, 0.01632 g) and added to the previous solution. The solution was protected with aluminum foil to avoid any light irradiation and stirred vigorously at room temperature for 3 hours; then stirred vigorously under UV (365nm, 13A, 182W) irradiation at room temperature for 5 hours until a purple-gray milky solution is obtained.
The solution in the schlang flask was then transferred to a centrifuge tube for centrifugation (15000 rpm). The product was treated by repeating the deionized water or isopropanol addition, centrifugation, waste liquid decanting and pH measurement until the pH became neutral (equal to 7). The catalyst was then transferred again to a schlenk flask at room temperature under nitrogen.
Another metal precursor is then added by the procedure described above.
The resulting catalyst was transferred to a clean round bottom flask, heated at 80 ℃ and evaporated by vacuum using a pump to dry the deionized water, and the dried catalyst was analyzed by TEM, ICP, UV-Vis spectroscopy (if needed) and stored in a sample bottle under argon.
Pd-Au/TiO 2 (FJ-056-470)
Weighing a mass of TiO 2 (P90, 0.9834 g) and added to a Schlenk flask under a nitrogen atmosphere.
Independent weighing of metal precursor AuCl 3 ·xH 2 O (Au 49wt% in AuCl) 3 ·xH 2 O, 0.01680 g) and H 2 PdCl 4 Precursor (H) 2 PdCl 4 0.025g/mL in dilute aqueous HCl -1 0.75 mL) and both were dissolved in deionized water (7.0 mL) and isopropanol (9.0 mL) and a precursor solution was prepared.(H 2 PdCl 4 The precursor is prepared by reacting PdCl 2 (0.1769 g) was dissolved in 37% (v/v) HCl (0.53 mL), and water was added to dilute the solution to 10 mL.
The metal precursor solution is then added to the solution containing TiO 2 And the solution was protected with aluminum foil to avoid any light irradiation, and it was vigorously stirred at room temperature for 3 hours.
The solution was then stirred vigorously at room temperature for 7 hours under UV (365nm, 13A, 182W) irradiation until a purple milky solution was obtained.
The solution in the schlank flask was then transferred to a centrifuge tube for centrifugation (15000 rpm). The product was treated by repeating the deionized water or isopropanol addition, centrifugation, waste liquid decanting and pH measurement until the pH became neutral (equal to 7). The catalyst was then transferred again to a schlenk flask at room temperature under nitrogen.
Another metal precursor is then added by the procedure described above.
The resulting catalyst was transferred to a clean round bottom flask, heated at 80 ℃ and evaporated by vacuum using a pump to dry the deionized water, and the dried catalyst was analyzed by TEM, ICP, UV-Vis spectroscopy (if needed) and stored in a sample bottle under argon.
TABLE 1 ICP results
Analyzing the device information:
perkin Elmer (Perkin Elmer) ICP-OES 8000
Electronic balance with 0.0001g accuracy
CEM 6 microwave oven
Moxa-moxibustion (IKA) heating plate
1mL pipette
100 muL pipette
50ml ICP tube
Software for ICP: winlab32 for ICP, version 5.4.0.0687
The analysis conditions are as follows:
-preparation: 50mg of sample are weighed and 3ml of H are added 3 PO 4 And 3ml of H 2 SO 4 Heated with a hot plate at 280C until the sample is completely dissolved, when the solution is left until 3-4ml, diluted with DI water and 10ppm Sc added as an internal standard solution to 50ml. Then diluted 10-fold to test for high concentration elements.
-reagents and solutions: distilled deionized ultra-high quality (UHQ chemical resistivity: 18M Ω cm) -1 ) Water (Millipore), phosphoric acid, analytical grade, 85%, sulfuric acid, analytical grade, 98% ICP, multi-element Standard solution IV, merck
-an instrument set-up: perkin Elmer 8000ICP-OES was used to determine the three elements. The operating parameters of the ICP-OES are set according to the manufacturer's recommendations. The operating conditions for ICP-OES are listed in Table 2.
TABLE 2 ICP operating parameters
Example 1:
an autoclave equipped with a quartz window, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then weighed the photocatalyst prepared by a different method described in table 3 (0.02 g) and then immediately transferred to a quartz vial, followed by the addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and rapidly evacuated 3 times, finally purged with 5 bar of hydrogen. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure was kept constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stir plate. After stirring, the UV lamp was turned on with a current of 13A and a power of 182W, and then the reaction was carried out at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully vented to hydrogen in a fume hood. Add internal standard biphenyl to the reaction mixture with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
TABLE 3
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
The method comprises the following steps: deposition-precipitation-reduction; the method 2 comprises the following steps: photo deposition method
Example 2:
an autoclave equipped with a quartz window, equipped with a cleaned vial made of quartz, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then weighed the photocatalyst (0.02 g) prepared by photo-deposition using different intensities of UV light as described in table 4 and then immediately transferred to a quartz vial, followed by addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and rapidly evacuated 3 times, finally purged with 5 bar of hydrogen. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure remained constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stirring plate. After stirring, the UV lamp was turned on with a current of 13A and a power of 182W, and the reaction was then carried out at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully vented to hydrogen in a fume hood. To the reaction mixture was added biphenyl, an internal standard, with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
TABLE 4
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
Example 3:
the catalysts were prepared using the various concentrations of palladium precursor described in table 5.
An autoclave equipped with a quartz window, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then the photocatalyst prepared by photo-deposition (0.02 g) was weighed and then immediately transferred into the quartz vial, followed by the addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and rapidly evacuated 3 times, finally purged with 5 bar of hydrogen. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure was kept constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stir plate. After stirring, the UV lamp was turned on with a current of 13A and a power of 182W, and then the reaction was carried out at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully vented to hydrogen in a fume hood. Add internal standard biphenyl to the reaction mixture with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
TABLE 5
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
Example 4:
the prepared catalyst was washed by centrifugation using different solvents after washing at different times as described in table 6.
An autoclave equipped with a quartz window, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then the photocatalyst prepared by photo-deposition (0.02 g) was weighed and then immediately transferred to the quartz vial, followed by the addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and evacuated rapidly 3 times, finally with 5 bar of hydrogen. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure remained constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stirring plate. After stirring, the UV lamp was turned on with a current of 13A and a power of 182W, and then the reaction was carried out at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully evacuated of hydrogen in a fume hood. Add internal standard biphenyl to the reaction mixture with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
TABLE 6
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
DI: deionised
Example 5:
an autoclave equipped with a quartz window, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then the photocatalyst prepared by photo-deposition with different palladium loadings described in table 7 (0.02 g) was weighed and then immediately transferred to a quartz vial, followed by addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and rapidly evacuated 3 times, finally purged with 5 bar of hydrogen. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure was kept constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stir plate. After stirring, the UV lamp was turned on with a current of 13A and a power of 182W, and the reaction was then carried out at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully vented to hydrogen in a fume hood. Add internal standard biphenyl to the reaction mixture with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
TABLE 7
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
Example 6:
an autoclave equipped with a quartz window, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then the photocatalyst prepared by photo-deposition using different supports described in table 8 (0.02 g) was weighed and then immediately transferred into a quartz vial, followed by the addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and rapidly evacuated 3 times, finally purged with 5 bar of hydrogen. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure remained constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stirring plate. After stirring, the UV lamp was turned on with a current of 13A and a power of 182W, and then the reaction was carried out at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully vented to hydrogen in a fume hood. Add internal standard biphenyl to the reaction mixture with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
TABLE 8
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
Example 7:
an autoclave equipped with a quartz window, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then weighed the photocatalyst prepared by photo-deposition method described in table 9 using different metal precursor combinations and resulting in different bimetallic catalysts (0.02 g) and then immediately transferred to a quartz vial, followed by the addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and evacuated rapidly 3 times, finally with 5 bar of hydrogen. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure was kept constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stir plate. After stirring, the UV lamp was turned on with a current of 13A and a power of 182W, and the reaction was then carried out at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully evacuated of hydrogen in a fume hood. To the reaction mixture was added biphenyl, an internal standard, with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
TABLE 9
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
Example 8:
an autoclave equipped with a quartz window, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then the photocatalyst prepared by photo-deposition (0.02 g) was weighed and then immediately transferred to the quartz vial, followed by the addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and rapidly evacuated 3 times, finally with hydrogen at various pressures as described in table 10. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure remained constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stirring plate. After stirring, the UV lamp was turned on with a current of 13A and a power of 182W, and then the reaction was carried out at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully vented to hydrogen in a fume hood. Add internal standard biphenyl to the reaction mixture with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
TABLE 10
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
Example 9:
an autoclave equipped with a quartz window, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then the photocatalyst prepared by photo-deposition (0.02 g) was weighed and then immediately transferred into the quartz vial, followed by the addition of methanol (0.06mol, 2.0 g) and different weights of octylamine according to the different mass ratios of catalyst to octylamine described in table 11 under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and rapidly evacuated 3 times, finally purged with 5 bar of hydrogen. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure was kept constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stir plate. After stirring, the UV lamp was switched on, with a current of 13
A, power 182W, then the reaction was run at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully vented to hydrogen in a fume hood. Add internal standard biphenyl to the reaction mixture with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
TABLE 11
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
Example 10:
an autoclave equipped with a quartz window, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then the photocatalyst prepared by photo-deposition (0.02 g) was weighed and then immediately transferred to the quartz vial, followed by the addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and rapidly evacuated 3 times, finally purged with 5 bar of hydrogen. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure was kept constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stirring plate. After stirring, the UV lamp was turned on with certain current and power as described in table 12, and then the reaction was carried out at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully evacuated of hydrogen in a fume hood. To the reaction mixture was added biphenyl, an internal standard, with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
TABLE 12
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
Example 11:
a glass-made schlank-type reactor equipped with a cylindrical PTFE magnetic stirrer, with a screw plug, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then the photocatalyst prepared by photo-deposition (0.02 g) was weighed and then immediately transferred into a quartz vial, followed by addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The reactor was well sealed under nitrogen and purged with argon 1atm for 1 minute and finally with hydrogen at 1 atmosphere. The reactor was sealed at room temperature without stirring.
The reactor, which was not equipped with a recirculating water cooling bath, was placed on a magnetic stirring plate. The reactor was then irradiated with a UV lamp without a 365nm filter. After stirring, the UV lamp was turned on with a power of 9W, and then the reaction was carried out at ambient temperature for a certain duration as described in table 13. The apparatus was then cooled and shut down and carefully evacuated of hydrogen in a fume hood. Add internal standard biphenyl to the reaction mixture with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
Watch 13
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
Example 12:
an autoclave equipped with a quartz window, equipped with a 6mm x 20mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, and then weighed to be prepared by the photo-deposition method0.55wt% of the photocatalyst of (2) 2 (P90) (0.026 g) and then immediately transferred to a quartz vial followed by addition of methanol (0.06mol, 2.0 g) and Diethylenetriamine (DETA) (0.25mmol, 0.026 g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and evacuated rapidly 3 times, finally with 5 bar of hydrogen. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure remained constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stirring plate. After stirring, the UV lamp was turned on with a current of 18A and a power of 252W, and then the reaction was carried out at ambient temperature for 40 hours. The apparatus was then cooled and shut down and carefully vented to hydrogen in a fume hood. To the reaction mixture was added biphenyl, an internal standard, with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration. The conversion of DETA was 98%. The yield of N, N, N', N "-Pentamethyldiethylenetriamine (PMDTA) was 60%.
Comparative example:
an autoclave equipped with a quartz window, equipped with a 6mm x 2mm cylindrical PTFE magnetic stirrer, containing a clean vial made of quartz, was charged under nitrogen after 3 exchanges of vacuum and nitrogen, then the photocatalyst prepared by photo-deposition (0.02 g) was weighed and then immediately transferred to the quartz vial, followed by the addition of methanol (0.06mol, 2.0 g) and octylamine (0.2mmol, 0.026g) under nitrogen.
The autoclave was well sealed under nitrogen and purged with nitrogen 1atm and evacuated rapidly 3 times, finally with hydrogen and argon at the various pressures described in table 14. The tightness of the reactor was checked by waiting 1 hour at room temperature without stirring and if the pressure was kept constant, the reactor was well sealed.
The window of the autoclave was then connected to a UV lamp equipped with a 365nm filter. The autoclave, equipped with a recirculating water cooling bath, was placed on a magnetic stirring plate. After stirring, the UV lamp was turned on with a current of 13A and a power of 182W, and the reaction was then carried out at ambient temperature for 2 hours. The apparatus was then cooled and shut down and carefully evacuated of hydrogen in a fume hood. Add internal standard biphenyl to the reaction mixture with the correct weight. After the biphenyl was completely dissolved, the liquid was first weighed and then filtered and analyzed by GC. Conversion and yield were calculated using internal standard calibration.
This table shows that higher OA conversion and alkylated amines were obtained by using hydrogen as the working atmosphere.
TABLE 14
OA-octylamine DMOA-dimethyloctylamine MOA-methyloctylamine
Claims (15)
1. A process for preparing alkylated amines by reacting a primary or secondary amine with an alcohol in the presence of hydrogen, a metal catalyst supported by a photosensitive titanium oxide, and UV irradiation.
2. The process according to claim 1, wherein the primary or secondary amine has the general formula (I):
R 1 R 2 NH (I)
wherein R is 1 And R 2 Independently of one another, represents hydrogen, or a linear, branched or cyclic hydrocarbon radical optionally interrupted by one or several heteroatoms and/or optionally substituted by one or several functional groups, R 1 And R 2 Is not simultaneousAre all hydrogen and the heteroatom is O, S, F, or N.
3. The process according to claim 1, wherein the primary or secondary amine has the general formula (II):
wherein:
-n is an integer between 0 and 20;
-m is an integer between 1 and 3;
-p is an integer between 0 and 2, and
-p+m＝3。
4. the method according to claim 3, wherein the compound of formula (II) is a compound of formula (III), (IV) or (V):
wherein n is an integer between 0 and 20.
5. The method according to claim 3 or 4, wherein the compound having general formula (II) is selected from the group consisting of: dimethylenetriamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, dihexylylenetriamine, diheptylenetriamine, dioctylenetriamine, dinonylenetriamine, didecylylenetriamine, methylenediamine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine and decylenediamine, triaminomethylamine, tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, tris (4-aminobutyl) amine, tris (5-aminopentyl) amine, tris (6-aminohexyl) amine, tris (7-aminoheptyl) amine, tris (8-aminooctyl) amine, tris (9-aminononyl) amine and tris (10-aminodecyl) amine.
6. The process according to claim 1, wherein the alcohol has the general formula (VI):
R 3 OH (VI)
wherein R is 3 Is alkyl, alkenyl or alkynyl.
7. The method according to any one of claims 1 to 6, wherein the metal catalyst comprises a noble metal selected from the group consisting of: palladium, gold, platinum, silver, and combinations thereof.
8. The method of any one of claims 1 to 7, wherein the photosensitive titanium oxide is a mixture of anatase and rutile crystals.
9. The method according to any one of claims 1 to 8, wherein the BET surface area of the crystals of the photosensitive titanium oxide is preferably from 10 to 600m 2 G and preferably from 30 to 400m 2 /g。
10. Process according to any one of claims 1 to 9, wherein the weight ratio of the supported metal catalyst to the primary or secondary amine is from 0.001 to 100 and preferably from 0.01 to 10.
11. Process according to any one of claims 1 to 10, wherein the weight ratio of the primary or secondary amine to the alcohol is from 0.0001 to 0.5 and preferably from 0.001 to 0.2.
12. Process according to any one of claims 1 to 11, wherein the reaction is carried out in the presence of a solvent and the concentration of the primary or secondary amine in the solvent is from 0.01 to 50% by weight and preferably from 0.1 to 20% by weight.
13. Process according to any one of claims 1 to 12, wherein the reaction is carried out at a hydrogen pressure in the range of 0.1 to 20 bar, and preferably 0.5 to 12 bar.
14. The process according to any one of claims 1 to 13, wherein the reaction temperature is from 0 ℃ to 100 ℃, preferably from 10 ℃ to 50 ℃ and more preferably room temperature.
15. A mixture, comprising:
(i) A primary or secondary amine, or a mixture thereof,
(ii) An alcohol in the form of a mixture of alcohols,
(iii) Hydrogen gas, and
(iv) A metal catalyst supported by a photosensitive titanium oxide.
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| PCT/CN2020/078160 WO2021174523A1 (en) | 2020-03-06 | 2020-03-06 | A method for preparing alkylated amines |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1984873A (en) * | 2004-05-13 | 2007-06-20 | 巴斯福股份公司 | Method for the continuous production of an amine |
| CN106986776A (en) * | 2017-03-29 | 2017-07-28 | 中国科学院化学研究所 | The method that aminated compounds N methylates is realized in a kind of utilization photocatalysis |
-
2020
- 2020-03-06 CN CN202080098306.9A patent/CN115244029A/en active Pending
- 2020-03-06 WO PCT/CN2020/078160 patent/WO2021174523A1/en unknown
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1984873A (en) * | 2004-05-13 | 2007-06-20 | 巴斯福股份公司 | Method for the continuous production of an amine |
| CN106986776A (en) * | 2017-03-29 | 2017-07-28 | 中国科学院化学研究所 | The method that aminated compounds N methylates is realized in a kind of utilization photocatalysis |
Non-Patent Citations (5)
| Title |
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| FENG SHI等: "Light-promoted N, N-dimethylation of amine and nitro compound with methanol catalyzed by Pd/ TiO2 at room temperature", RSC ADVANCES, vol. 5, 31 December 2015 (2015-12-31), pages 14514 * |
| HUANG, JIA-MIN等: "N-alkylation of ethylenediamine with alcohols catalyzed by CuO-NiO/γ-Al2O3", CHEMICAL PAPERS, vol. 66, no. 4, 31 December 2012 (2012-12-31), pages 304 - 307, XP035021878, DOI: 10.2478/s11696-012-0140-8 * |
| JEROEN A. VAN BOKHOVEN等: "One-pot photo-reductive N-alkylation of aniline and nitroarene derivatives with primary alcohols over Au–TiO2", CATAL. SCI. TECHNOL, vol. 3, 31 December 2013 (2013-12-31), pages 94 - 98, XP055842312, DOI: 10.1039/C2CY20511D * |
| OHTANI, BUNSHO等: "A novel photocatalytic process of amine N-alkylation by platinized semiconductor particles suspended in alcohols", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 108, no. 2, 31 December 1986 (1986-12-31), pages 309, XP093105511, DOI: 10.1021/ja00262a028 * |
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