CN116621736A - 一种异氰酸酯类化合物的制备方法 - Google Patents
一种异氰酸酯类化合物的制备方法 Download PDFInfo
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- CN116621736A CN116621736A CN202310562798.8A CN202310562798A CN116621736A CN 116621736 A CN116621736 A CN 116621736A CN 202310562798 A CN202310562798 A CN 202310562798A CN 116621736 A CN116621736 A CN 116621736A
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 14
- -1 isocyanate compound Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005580 one pot reaction Methods 0.000 claims abstract description 9
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- NXLNNXIXOYSCMB-UHFFFAOYSA-N (4-nitrophenyl) carbonochloridate Chemical compound [O-][N+](=O)C1=CC=C(OC(Cl)=O)C=C1 NXLNNXIXOYSCMB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims 1
- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical compound O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 125000003118 aryl group Chemical class 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- KATOLVAXCGIBLO-UHFFFAOYSA-N 1,3-dibenzylurea Chemical compound C=1C=CC=CC=1CNC(=O)NCC1=CC=CC=C1 KATOLVAXCGIBLO-UHFFFAOYSA-N 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QRBHVARIMDDOOV-UHFFFAOYSA-N 1-(isocyanatomethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CN=C=O)C=C1 QRBHVARIMDDOOV-UHFFFAOYSA-N 0.000 description 2
- KNYDWDHLGFMGCO-UHFFFAOYSA-N 1-(isocyanatomethyl)-4-methylbenzene Chemical compound CC1=CC=C(CN=C=O)C=C1 KNYDWDHLGFMGCO-UHFFFAOYSA-N 0.000 description 2
- HHSIWJYERNCLKQ-UHFFFAOYSA-N 1-fluoro-4-(isocyanatomethyl)benzene Chemical compound FC1=CC=C(CN=C=O)C=C1 HHSIWJYERNCLKQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- IIFVWLUQBAIPMJ-UHFFFAOYSA-N (4-fluorophenyl)methanamine Chemical compound NCC1=CC=C(F)C=C1 IIFVWLUQBAIPMJ-UHFFFAOYSA-N 0.000 description 1
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 description 1
- IDPURXSQCKYKIJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/06—Preparation of derivatives of isocyanic acid from or via ureas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/10—Formation or introduction of functional groups containing nitrogen of isocyanate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/48—Aldehydo radicals
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/50—Ketonic radicals
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
本发明涉及异氰酸酯类化合物的制备方法,特别涉及芳基或杂环类异氰酸酯衍生物的制备方法。以胺类化合物为原料,经缩合和水解反应制备异氰酸酯类化合物。反应式为:
Description
技术领域
本发明涉及异氰酸酯类化合物的制备方法,特别涉及芳基或杂环类异氰酸酯衍生物的制备方法。
背景技术
异氰酸酯是一类重要的有机反应中间体,它在工业、农业、医药卫生等方面都有非常广泛的用途,是合成高聚物粘合剂、杀虫剂、除草剂等材料的重要原料。目前国际上异氰酸酯年产量上百万吨,是一类有重要影响的基础有机化学品。
其合成方法一般是通过三光气与胺反应来合成。具体技术方案如下:
可参见中国专利CN104292170A。该工艺收率99%,但是三光气是一种高毒性且价格昂贵的试剂,在生产过程中产生的废弃物会腐蚀设备,一旦泄露会造成人员伤亡和环境污染,对生产设备要求高。
另一种方法是通过硝基化合物的还原羰化法来合成二取代脲,再通过热解来制备异氰酸苄酯,此工艺虽然避免使用高毒性的光气,但是需要使用到贵金属作为催化剂,还需要在高温高压的条件下进行。
在此基础上中国专利CN1966491A公开了另一种合成工艺。用尿素与苄胺按1:4的比例混合,以反应物为溶剂,在常压下将温度升到160℃,反应时间为420分钟,得到二苄基脲收率为95%,然后再将二苄基脲在250℃下热解,精馏得到的异氰酸苄酯收率为45%。具体技术方案如下:
该路线虽然避免了使用贵金属催化剂,且反应过程中生产的氨气和胺都可以循环利用,但是此条件反应温度高,反应周期长,收率低对工业化生产设备要求高。
鉴于现有的技术报导对于异氰酸酯及衍生物的工艺存在的缺点,不适于工业化放大生产,有必要开发具备技术优势的工艺路线,克服反应条件剧烈,绿色环保的工业化生产工艺。
发明内容
为了克服现有技术中存在的技术问题,本发明提供了一种芳基及杂环类衍生物的制备方法。为实现本发明的技术目的,本发明的技术方案为:
首先,本发明提供了一类芳基类及吡啶环类异氰酸酯化合物,其结构通式如下:
其中
R=H,-F,-Cl,-Br,-I,-CH3,-OCH3,-COOCH3,-NHCOCH3,-OCOCH3,-NO2,-SO2CH3,-CHO或-COCH3。
本发明进一步提供了上述化合物的制备方法,包括两步反应:第一步为缩合生成活性酰胺,第二步酸水解反应热解得到化合物。反应式如下:
其中R1为咪唑基团、烷氧基、芳环氧基等。
所述缩合反应在缩合剂存在条件下进行,所述缩合剂可以为羰基二咪唑、氯甲酸甲酯、氯甲酸乙酯、对硝基苯基氯甲酸酯、三光气等,本发明较优选择羰基二咪唑。
所述缩合反应后产物进一步与酸水解反应,所述使用的酸为甲基磺酸、乙基磺酸、对甲苯磺酸等。较优选择为甲基磺酸。
本发明两步反应可以采用“一锅法”进行。
所述“一锅法”所使用的反应溶剂可以为:乙腈、二氧六环、2-甲基四氢呋喃等,较优选择为乙腈。
所述“一锅法”反应温度包括阶段式升温:第一阶段温度为20-25℃;第二阶段温度为70-75℃。
本发明较优选的一种实施方式为:以苄胺为原料,通过羰基二咪唑缩合再经过甲基磺酸水解后热解来制备异氰酸苄酯。具体技术方案如下:
本发明以苄胺为原料,通过缩合、水解、热解的“一锅法”制备异氰酸苄酯,收率高,原料成本低,反应周期短,反应条件温和,绿色环保,可以实现工业化生产。
具体实施方式
通过以下实施例进一步详细说明本发明,但应注意本发明的范围并不受这些实施例的任何限制。
本发明所使用的试剂均可以从市场上购得。
本发明中mol表示摩尔,h表示小时,min表示分钟,g表示克,L表示升,ml表示毫升。
实施例1:以苄胺为原料合成异氰酸苄酯
氮气保护下,2000ml的四口瓶中加入羰基二咪唑(83.22g 0.51mol)和乙腈(250ml5Vol),控制温度在20-25℃,滴加苄胺(50.00g 0.47mol)的乙腈(150ml 3Vol)溶液,滴加时间1.0-1.5h,滴加完毕,在20-25℃搅拌反应1-2h(GC检测),控制20-25℃下滴加甲磺酸(98.66g 1.03mol)的乙腈(100ml 2Vol)溶液,滴加时间为1-1.5h,滴加完毕后,保温15-20min后升温到70-75℃保温1-2h(GC检测)。反应结束后滴加甲苯(400ml 8Vol),滴加结束后降温到20-25℃保温搅拌0.5-1h,过滤,滤饼用甲苯(400ml 8Vol)打浆,过滤,合并滤液,水泵45-50℃蒸干得到油状物。将油状物油泵减压蒸馏,收集40-45℃馏分,得到淡黄色液体57.78g,收率93%。
实施例2:同实施例1操作,以4-甲基苄胺为原料合成4-甲基苄基异氰酸酯,收率为92.8%。实施例3:同实施例1操作,以4-甲氧基苄胺为原料合成4-甲氧基苄基异氰酸酯,收率90.4%。实施例4:同实施例1操作,以对氟苄胺为原料合成4-氟苄基异氰酸酯,收率89.3%。
异氰酸苄酯结构信息:
1H NMR(400MHz,DMSO-d6):δ7.44-7.23(m,5H),4.58(s,2H)
4-甲基苄基异氰酸酯结构信息:
1H NMR(400MHz,DMSO-d6):δ7.29-7.17(m,4H)4.53(s,2H)2.30(s,3H)
4-甲氧基苄基异氰酸酯结构信息:
1H NMR(400MHz,DMSO-d6):δ7.36-7.25(m,2H),6.98-6.86(m,2H),4.48(s,2H),3.75(s,3H)
4-氟苄基异氰酸酯结构信息:
1H NMR(400MHz,DMSO-d6):δ7.29(d,8Hz,2H),7.25(d,8Hz,2H),4.22(s,2H)
尽管已经结合了具体实施方式对本发明进行了充分的描述,应当注意的是对于本领域技术人员来说其各种变化和修改是显而易见的。这样的变化和修改将可以理解为包括在由所附权利要求所定义的本发明的范围内。
Claims (10)
1.一种异氰酸酯类化合物的制备方法,其特征在于,经缩合反应和水解反应制备,
其中,R=H,-F,-Cl,-Br,-I,-CH3,-OCH3,-COOCH3,-NHCOCH3,-OCOCH3,-NO2,-SO2CH3,-CHO或-COCH3,R1为咪唑基团、烷氧基或芳环氧基。
2.根据权利要求1所述的制备方法,其特征在于,所述缩合反应和水解反应两步反应采用“一锅法”进行。
3.根据权利要求1所述的制备方法,其特征在于,所述“一锅法”反应的中间态化合物结构式为:
4.根据权利要求1所述的制备方法,其特征在于,R为H,R1为咪唑。
5.根据权利要求1或2所述的制备方法,其特征在于,所述缩合反应中缩合剂为羰基二咪唑、氯甲酸甲酯、氯甲酸乙酯、对硝基苯基氯甲酸酯或三光气。
6.根据权利要求1或2所述的制备方法,其特征在于,所述水解反应通过酸水解。
7.根据权利要求6所述的制备方法,其特征在于,所述酸为甲基磺酸、磺酰氯、乙基磺酸或对甲苯磺酸。
8.根据权利要求2所述的制备方法,其特征在于,所述一锅法所使用的反应溶剂为乙腈、二氧六环或2-甲基四氢呋喃。
9.根据权利要求2所述的制备方法,其特征在于,所述一锅法反应的反应温度经历阶段式升温。
10.根据权利要求9所述的制备方法,其特征在于,所述阶段式升温包括第一阶段温度为20-25℃,第二阶段温度为70-75℃。
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