CN110483332A - 2,6-二氯氯苄氨碘化法制备2,6-二氯苯腈的方法 - Google Patents
2,6-二氯氯苄氨碘化法制备2,6-二氯苯腈的方法 Download PDFInfo
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- CN110483332A CN110483332A CN201910728281.5A CN201910728281A CN110483332A CN 110483332 A CN110483332 A CN 110483332A CN 201910728281 A CN201910728281 A CN 201910728281A CN 110483332 A CN110483332 A CN 110483332A
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- ammonium
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- dichlorobenzonitrile
- chloride
- ammonia
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- 238000000034 method Methods 0.000 title claims abstract description 56
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- -1 2,6- dichlorobenzyl chloride ammonia iodide Chemical compound 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- LBOBESSDSGODDD-UHFFFAOYSA-N 1,3-dichloro-2-(chloromethyl)benzene Chemical compound ClCC1=C(Cl)C=CC=C1Cl LBOBESSDSGODDD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 17
- 239000011630 iodine Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 11
- 230000036571 hydration Effects 0.000 claims abstract description 10
- 238000006703 hydration reaction Methods 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 239000003444 phase transfer catalyst Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical group [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- 229940107816 ammonium iodide Drugs 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 229940057874 phenyl trimethicone Drugs 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- LINXHFKHZLOLEI-UHFFFAOYSA-N trimethyl-[phenyl-bis(trimethylsilyloxy)silyl]oxysilane Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)C1=CC=CC=C1 LINXHFKHZLOLEI-UHFFFAOYSA-N 0.000 claims description 2
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000006073 displacement reaction Methods 0.000 description 7
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- QQPXXHAEIGVZKQ-UHFFFAOYSA-N 1,3-dichloro-2-(dichloromethyl)benzene Chemical compound ClC(Cl)C1=C(Cl)C=CC=C1Cl QQPXXHAEIGVZKQ-UHFFFAOYSA-N 0.000 description 2
- RDZHCKRAHUPIFK-UHFFFAOYSA-N 1,3-diiodo-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(I)C(=O)N(I)C1=O RDZHCKRAHUPIFK-UHFFFAOYSA-N 0.000 description 2
- GRUHREVRSOOQJG-UHFFFAOYSA-N 2,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C(Cl)=C1 GRUHREVRSOOQJG-UHFFFAOYSA-N 0.000 description 2
- KUWBYWUSERRVQP-UHFFFAOYSA-N 3,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1Cl KUWBYWUSERRVQP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007333 cyanation reaction Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- YBSXDWIAUZOFFV-ONNFQVAWSA-N (ne)-n-[(2,6-dichlorophenyl)methylidene]hydroxylamine Chemical compound O\N=C\C1=C(Cl)C=CC=C1Cl YBSXDWIAUZOFFV-ONNFQVAWSA-N 0.000 description 1
- ONJQBRVMFRQQIG-WMZJFQQLSA-N (nz)-n-[(2,4-dichlorophenyl)methylidene]hydroxylamine Chemical compound O\N=C/C1=CC=C(Cl)C=C1Cl ONJQBRVMFRQQIG-WMZJFQQLSA-N 0.000 description 1
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 1
- YSFBEAASFUWWHU-UHFFFAOYSA-N 2,4-dichlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C(Cl)=C1 YSFBEAASFUWWHU-UHFFFAOYSA-N 0.000 description 1
- ODUZJBKKYBQIBX-UHFFFAOYSA-N 2,6-difluoroaniline Chemical compound NC1=C(F)C=CC=C1F ODUZJBKKYBQIBX-UHFFFAOYSA-N 0.000 description 1
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004803 chlorobenzyl group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- RYLHNOVXKPXDIP-UHFFFAOYSA-N flufenoxuron Chemical compound C=1C=C(NC(=O)NC(=O)C=2C(=CC=CC=2F)F)C(F)=CC=1OC1=CC=C(C(F)(F)F)C=C1Cl RYLHNOVXKPXDIP-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种2,6‑二氯氯苄氨碘化法制备2,6‑二氯苯腈的方法,该方法综合分析制备2,6‑二氯苯腈的方法的基础上,利用卤素单质进行清洁氧化转换,提出以2,6‑二氯氯苄为原料,使用卤素单质作为氧化剂,经氨碘化一步法制备2,6‑二氯苯腈的方法。与传统工艺相比本方法催化剂简单、能耗低、生产更易控制、无副产物、环境污染小等,因而从多个方面降低工业成本,提高工业生产效率。本发明的2,6‑二氯氯苄氨碘化法制备2,6‑二氯苯腈的方法,其是以2,6‑二氯氯苄为原料,以单质碘为氧化剂,以氨水为溶剂,加入催化剂,在20‑150℃的水合釜中反应0.1‑18h,经分离得到2,6‑二氯苯腈。
Description
技术领域
本发明涉及一种化工原料2,6-二氯苯腈的制备方法,更具体地说涉及一种2,6-二氯氯苄氨碘化法制备2,6-二氯苯腈的方法。
背景技术
2,6-二氯苯腈是一种重要的合成转化前体,尤其是在酯、酰胺、羧酸、胺和含氮杂环的合成中。其已被广泛用于农业化学品、药物化学品和功能材料化学品中间体的合成,被广泛应用于生产2,6-二氟苯腈、2,6-二氟苯胺、草克乐、氟虫脲等。2,6-二氯苯腈还是一种优良的除草剂,对一年生和多年生的杂草有着表现出极好的抑制效果。
2,6-二氯苯腈合成方法众多,根据原料不同可分为如下几类:
(1)苯胺重氮化法
李新颖等(李新颖,祁同生,聂丰秋,王艳辉,林秀荣.2,6-二氯苯甲腈的合成路线[J].河北化工,1996(03):40-43.)在2,6-二氯苯甲腈的合成路线中提到,以2,6-二氯苯胺为原料,经重氮化、腈化反应制得2,6-二氯苯腈。但,2,6-二氯苯胺不易得到、价格昂贵,且使用剧毒的腈化物。故该路线只适用于实验室内小批量合成2,6-二氯苯腈。
(2)羟胺肟化法
2,6-二氯甲苯或2-氯-6-硝基甲苯侧链氯化生成2,6-二氯苄叉二氯,在最新的研究进展中也采用在光和五氯化磷的作用下制备2,6-二氯氯苄。在氯化锌和一水合苯磺酸的存在下进行水解生成2,6-二氯苯甲醛,与盐酸羟胺反应后生成2,6-二氯苯甲醛肟,经脱水后可得最终产物2,6-二氯苯腈。专利(CN103382166.A)公开了一种制备2,6-二氯苯腈的方法,使用2,6-二氯甲苯为原料,在五氯化磷和光的催化作用下进行氯化反应得到2,6-二氯苄叉二氯,再经水解、腈化得到2,6-二氯苯甲腈粗品后精制,纯度在99.8-99.95%。专利(CN1775747.A)公开了2,6-二氯苯腈工业化生产的方法,以6-氯-2-硝基甲苯为原料,在五氯化磷以及吡啶的作用下与氯气发生反应生成2,6-二氯苄后,与甲酸和氯化锌生成2,6-二氯苯甲醛。再与盐酸羟胺进行腈化反应,精制后获得含量99.8%以上的2,6-二氯苯腈。专利(CN103588679.A)公开了一种2,4-二氯苯腈的合成方法,将2,4-二氯苯甲醛与盐酸羟胺进行混合,在70~75℃下反应20~40min,得到乳白色固体粉末2,4-二氯苯甲醛肟。再与醋酸酐进行混合,在110~120℃下反应2~4h,得到2,4-二氯苯腈,收率90%。
(3)2,6-二氯甲苯氨氧化法
以2,6-二氯甲苯为原料,与氨气、空气按照一定比例进入固定床反应器中,于300~500℃下反应。此方法所需能耗较高,且反应后的冷却步骤延长了反应周期。专利(CN1230537.A)公开了用于制备2,6-二氯苯甲腈工艺,以2,6-二氯甲苯、氨气和氧气为原料,以V-P-Na体系的组合物为催化剂进行反应,反应过程中添加溴或溴化合物。
专利(CN102603569.A)公开了一种3,4-二氯苯腈的生产方法,将固定床内填入催化剂(将氧化钠、氯化钡、二氧化硅、氧化锶和氧化钙按一定比例混合,并在110~130℃下预处理6~12h成型,再经600~750℃烧结8~12h),再将催化剂在320~420℃下通氧预处理10~14h,然后用泵注入3,4-二氯甲苯的同时通入氨气,即得到3,4-二氯苯腈粗品,收率在88%以上。
(4)2,6-二氯氯苄氨氧化法
专利(CN108774156.A)公开了一种制备2,6-二氯苯甲腈的方法,以2,6-二氯氯苄为原料,采用气相氨氧化法,催化剂为自制DBN-1,在390℃下反应后,再经过降温、水洗、离心脱水得到2,6-二氯苯甲腈粗品。专利(CN109046454.A)公开了一种用于合成合成2,6-二氯苯甲腈的催化剂及其制备方法,该催化剂可用于2,6-二氯甲苯或2,6-二氯氯苄为原料制备2,6-二氯苯甲腈的反应,还可减少2,6-二氯氯苄的过度氧化,2,6-二氯苯腈收率最高为89.2%。
综上所述,羟胺肟化法路线较长,反应所需能耗大、催化剂较多,氯化过程中产生较多副产物,总收率偏低;2,6-二氯甲苯氨氧化法所需的催化剂成分极为复杂,且合成步骤较为繁琐,导致生产成本较高;2,6-二氯氯苄氨氧化法所需的催化剂制备工艺复杂,生产过程不易控制、能耗偏高。无论是从能源、环保、安全方面还是经济成本方面考虑,急需开发新的生产工艺。
单质碘是目前可用的最简单的氧化剂之一,具有反应条件温和、廉价且易于获得等特点,常用于各种有机合成反应中。Shinpei Iida和Hideo Togo等(Shinpei Iida,Direct oxidative conversion of alkyl halides into nitriles with moleculariodine and 1,3-diiodo-5,5-dimethylhydantoin in aq ammonia.Tetrahedron 2009,65(31):6257-6262和Iida,Shinpei,and Hideo Togo,Direct oxidative conversion ofalcohols and amines to nitriles with molecular iodine and DIH in aqNH3.Tetrahedron 2007,63(34):8274-8281)致力于将氨基或卤代苄基氧化成腈基的研究,使用单质碘或琥珀酰亚胺等氧化剂将具有氨基或氯代苄基的有机物氧化成对应的腈基。因此,需要研制开发一种利用卤素单质制备2,6-二氯苯腈的方法的新方法。
发明内容
本发明针对现有技术的问题与不足,提供一种2,6-二氯氯苄氨碘化法制备2,6-二氯苯腈的方法,该方法综合分析制备2,6-二氯苯腈的方法的基础上,利用卤素单质进行清洁氧化转换,提出以2,6-二氯氯苄为原料,使用卤素单质作为氧化剂,经氨碘化一步法制备2,6-二氯苯腈的方法。与传统工艺相比本方法催化剂简单、能耗低、生产更易控制、无副产物、环境污染小等,因而从多个方面降低工业成本,提高工业生产效率。
本发明是通过以下技术方案实现的:
本发明的2,6-二氯氯苄氨碘化法制备2,6-二氯苯腈的方法,其是以2,6-二氯氯苄为原料,以单质碘为氧化剂,以氨水为溶剂,加入催化剂,在20-150℃的水合釜中反应0.1-18h,经分离得到2,6-二氯苯腈。具体是将2,6-二氯氯苄、单质碘、氨水、催化剂、铵盐,加入到反应釜中。密封反应釜后,开启搅拌,氮气置换空气三次。升温至目标温度,反应结束后打开反应釜,即可得到2,6-二氯苯腈。
本发明上述的方法,其进一步的技术方案是所述的催化剂为铵盐类催化剂或相转移催化剂,使用铵盐类催化剂时,其原料摩尔比为2,6-二氯氯苄:单质碘:氨:铵盐催化剂=1:15-35:5-45:0.1-4;使用相转移催化剂时,其原料摩尔比为2,6-二氯氯苄:单质碘:氨:相转移催化剂=1:15-35:5-45:0.001-0.1。
本发明上述的方法,其再进一步的技术方案是所述的铵盐类催化剂为氯化铵、碘化铵、氟化铵、硫酸铵、硝酸铵、碳酸铵、碳酸氢铵、溴化铵、甲酸铵或醋酸铵。
本发明上述的方法,其进一步的技术方案还可以是所述的相转移催化剂为季铵盐类或叔胺类催化剂。更进一步的技术方案是所述的相转移催化剂为四甲基氯化铵、四乙基氯化铵、苯基三甲基氯化铵、苯基三乙基氯化铵、十六烷基三甲基氯化铵、四丁基硫酸氢铵、四甲基溴化铵、四乙基溴化铵、四丙基溴化铵、四丁基溴化铵、十烷基三甲基溴化铵、十二烷基三甲基溴化铵或十六烷基三甲基溴化铵。
本发明上述的方法,其进一步的技术方案还可以是所述的反应时的温度为50-80℃。
本发明上述的方法,其进一步的技术方案还可以是所述的反应时间为5-11h。
本发明上述的方法,其再进一步的技术方案还可以是所述的使用铵盐类催化剂时,其原料摩尔比为2,6-二氯氯苄:卤素单质:氨:铵盐催化剂=1:20-30:5-40:0.5-3;使用相转移催化剂时,其原料摩尔比为2,6-二氯氯苄:卤素单质:氨:相转移催化剂=1:20-30:5-40:0.005-0.1。
本发明与现有技术相比具有以下有益效果:
本发明的方法具有工艺路线较短,原料易得,催化剂简单,生产控制简单,能耗低,收率高,无副产物污染小,从多个方面降低工业成本,可提高工业生产效率,适合工业化生产。
具体实施方式
实施例1
在150mL水合釜内,加入2,6-二氯氯苄2g、氨水60mL、碘单质7.62g、十六烷基三甲基氯化铵0.6g。密封反应釜后开启搅拌,使用氮气置换三次。升温至70℃,反应时间为9h,得到2,6-二氯苯腈的收率为97.7%。
实施例2
在150mL水合釜内,加入2,6-二氯氯苄2g、氨水60mL、碘单质7.62g、四甲基氯化铵0.6g。密封反应釜后开启搅拌,使用氮气置换三次。升温至70℃,反应时间为9h,得到2,6-二氯苯腈的收率为97.5%。
实施例3
在150mL水合釜内,加入2,6-二氯氯苄2g、氨水60mL、碘单质7.62g、碘化铵7.25g。密封反应釜后开启搅拌,使用氮气置换三次。升温至70℃,反应时间为9h,得到2,6-二氯苯腈的收率为97.4%。
实施例4
在150mL水合釜内,加入2,6-二氯氯苄2g、氨水60mL、碘单质7.62g、氯化铵5.35g。密封反应釜后开启搅拌,使用氮气置换三次。升温至70℃,反应时间为9h,得到2,6-二氯苯腈的收率为96.8%。
实施例5
在150mL水合釜内,加入2,6-二氯氯苄2g、氨水60mL、碘单质7.62g、乙酸铵7.71g。密封反应釜后开启搅拌,使用氮气置换三次。升温至70℃,反应时间为9h,得到2,6-二氯苯腈的收率为95.0%。
对比例1
在150mL水合釜内,加入2,6-二氯氯苄2g、氨水60mL、碘单质5.08g。密封反应釜后开启搅拌,使用氮气置换三次。升温至80℃,反应时间为5h,得到2,6-二氯苯腈的收率为45.8%。
对比例2
在150mL水合釜内,加入2,6-二氯氯苄2g、氨水60mL、碘单质7.62g。密封反应釜后开启搅拌,使用氮气置换三次。升温至70℃,反应时间为9h,得到2,6-二氯苯腈的收率为74.3%。
从对比例可以看出本发明的方法其收率远远大于现有技术。
Claims (8)
1.一种2,6-二氯氯苄氨碘化法制备2,6-二氯苯腈的方法,其特征在于该方法是以2,6-二氯氯苄为原料,以单质碘为氧化剂,以氨水为溶剂,加入催化剂,在20-150℃的水合釜中反应0.1-18h,经分离得到2,6-二氯苯腈。
2.根据权利要求1所述的方法,其特征在于所述的催化剂为铵盐类催化剂或相转移催化剂,使用铵盐类催化剂时,其原料摩尔比为2,6-二氯氯苄:单质碘:氨:铵盐催化剂=1:15-35:5-45:0.1-4;使用相转移催化剂时,其原料摩尔比为2,6-二氯氯苄:单质碘:氨:相转移催化剂=1:15-35:5-45:0.001-0.1。
3.根据权利要求2所述的方法,其特征在于所述的铵盐类催化剂为氯化铵、碘化铵、氟化铵、硫酸铵、硝酸铵、碳酸铵、碳酸氢铵、溴化铵、甲酸铵或醋酸铵。
4.根据权利要求2所述的方法,其特征在于所述的相转移催化剂为季铵盐类或叔胺类催化剂。
5.根据权利要求4所述的方法,其特征在于所述的相转移催化剂为四甲基氯化铵、四乙基氯化铵、苯基三甲基氯化铵、苯基三乙基氯化铵、十六烷基三甲基氯化铵、四丁基硫酸氢铵、四甲基溴化铵、四乙基溴化铵、四丙基溴化铵、四丁基溴化铵、十烷基三甲基溴化铵、十二烷基三甲基溴化铵或十六烷基三甲基溴化铵。
6.根据权利要求1所述的方法,其特征在于所述的反应时的温度为50-80℃。
7.根据权利要求1所述的方法,其特征在于所述的反应时间为5-11h。
8.根据权利要求2所述的方法,其特征在于所述的使用铵盐类催化剂时,其原料摩尔比为2,6-二氯氯苄:卤素单质:氨:铵盐催化剂=1:20-30:5-40:0.5-3;使用相转移催化剂时,其原料摩尔比为2,6-二氯氯苄:卤素单质:氨:相转移催化剂=1:20-30:5-40:0.005-0.1。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111233705A (zh) * | 2020-03-02 | 2020-06-05 | 南京工业大学 | 一种苄基氯衍生物氨氧化法制备相应苯腈的方法 |
CN114277388A (zh) * | 2021-12-24 | 2022-04-05 | 浙江工业大学 | 一种通过电化学原位生成ch3cooi催化合成2,6-二氯苯甲腈的方法 |
CN114950279A (zh) * | 2022-06-21 | 2022-08-30 | 江西国化实业有限公司 | 一种2,6-二氟苯甲腈制备用反应釜及生产工艺 |
-
2019
- 2019-08-08 CN CN201910728281.5A patent/CN110483332B/zh active Active
Non-Patent Citations (2)
Title |
---|
SHINPEI IIDA ET AL: "Direct oxidative conversion of alkyl halides into nitriles with molecular iodine and 1,3-diiodo-5,5-dimethylhydantoin in aq ammonia", 《TETRAHEDRON》 * |
刘鹰翔等: "《药物合成反应》", 31 August 2017, 中国中医药出版社 * |
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---|---|---|---|---|
CN111233705A (zh) * | 2020-03-02 | 2020-06-05 | 南京工业大学 | 一种苄基氯衍生物氨氧化法制备相应苯腈的方法 |
CN114277388A (zh) * | 2021-12-24 | 2022-04-05 | 浙江工业大学 | 一种通过电化学原位生成ch3cooi催化合成2,6-二氯苯甲腈的方法 |
CN114950279A (zh) * | 2022-06-21 | 2022-08-30 | 江西国化实业有限公司 | 一种2,6-二氟苯甲腈制备用反应釜及生产工艺 |
CN114950279B (zh) * | 2022-06-21 | 2023-12-08 | 江西国化实业有限公司 | 一种2,6-二氟苯甲腈制备用反应釜及生产工艺 |
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