CN105732392A - Method for preparing 4'-chloro-2-nitrobiphenyl - Google Patents
Method for preparing 4'-chloro-2-nitrobiphenyl Download PDFInfo
- Publication number
- CN105732392A CN105732392A CN201610172604.3A CN201610172604A CN105732392A CN 105732392 A CN105732392 A CN 105732392A CN 201610172604 A CN201610172604 A CN 201610172604A CN 105732392 A CN105732392 A CN 105732392A
- Authority
- CN
- China
- Prior art keywords
- chloro
- nitro biphenyl
- method preparing
- chloronitrobenzene
- reaction
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 22
- OMNWKPZIFZJANV-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=C(Cl)C=C1 OMNWKPZIFZJANV-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- QIFZRTGHATXWQI-UHFFFAOYSA-N 1-chloro-2-nitro-3-phenylbenzene Chemical group [O-][N+](=O)C1=C(Cl)C=CC=C1C1=CC=CC=C1 QIFZRTGHATXWQI-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- -1 chlorine trifluoro-benzene potassium borate Chemical compound 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 150000002941 palladium compounds Chemical class 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 150000002940 palladium Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000005740 Boscalid Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 claims description 4
- 229940118790 boscalid Drugs 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical group [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- BVZSQTRWIYKUSF-UHFFFAOYSA-N 4-(N-hydroxy-C-methylcarbonimidoyl)phenol Chemical compound ON=C(C)C1=CC=C(O)C=C1 BVZSQTRWIYKUSF-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002027 dichloromethane extract Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229940049953 phenylacetate Drugs 0.000 description 3
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 3
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical compound ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- SFUIGUOONHIVLG-UHFFFAOYSA-N (2-nitrophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1[N+]([O-])=O SFUIGUOONHIVLG-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- RXTRRIFWCJEMEL-UHFFFAOYSA-N 2-chloropyridine-3-carbonyl chloride Chemical compound ClC(=O)C1=CC=CN=C1Cl RXTRRIFWCJEMEL-UHFFFAOYSA-N 0.000 description 1
- AAQYVPPXHDPDOV-UHFFFAOYSA-N 2-nitrobenzoic acid;potassium Chemical compound [K].OC(=O)C1=CC=CC=C1[N+]([O-])=O AAQYVPPXHDPDOV-UHFFFAOYSA-N 0.000 description 1
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKUSWAGOKUGEDX-UHFFFAOYSA-N C(CCC)Br(CCCC)(CCCC)CCCC Chemical compound C(CCC)Br(CCCC)(CCCC)CCCC OKUSWAGOKUGEDX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000005784 autoimmunity Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- HORRDWBRNSMTIZ-UHFFFAOYSA-N diphenoxyborinic acid Chemical class C=1C=CC=CC=1OB(O)OC1=CC=CC=C1 HORRDWBRNSMTIZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for preparing 4'-chloro-2-nitrobiphenyl. The method comprises the following steps: o-chloronitrobenzene and p-chloro potassium benzyltrifluoroborate are adopted as raw materials which are added with a phase transfer catalyst and a palladium catalyst; and the 4'-chloro-2-nitrobiphenyl is obtained through reactions in an aqueous solution under a heating condition, wherein the reactions are carried out under a weak-base condition. The preparation method provided by the invention has the advantages of simplicity in operation, easily available raw materials, little environmental pollution, high yield, relatively good product quality and the like.
Description
Technical field
The invention belongs to industrial chemicals preparing technical field, especially relate to Boscalid intermediate 4'-chlorine
The preparation method of-2 nitro biphenyl.
Background technology
Chinese patent CN201310487320.X discloses the chloro-2 nitro biphenyl of 4'-after reduction nitro
Obtain 4'-chloro-2-aminobphenyl, then antibacterial Boscalid can be obtained with the reaction of 2-chloronicotinoyl chloride.Cause
This, the chloro-2 nitro biphenyl of 4'-is the important intermediate of Novel tobacco acid amide fungicides Boscalid, and it is prepared
The research of method is the most important.
The preparation method of the chloro-2 nitro biphenyl of 4'-, reports there is following report at present:
1) Chinese patent CN201410711705.4 mentions halobenzene boric acid or halogenated diphenyl boric acid and neighbour
Under halogen Nitrobenzol heating condition in a solvent, reaction obtains the chloro-2 nitro biphenyl of 4'-, can only select in reaction
Bromo-derivative or chloro thing；Though low cost simultaneously yield the lowest, reaction easily generates autoimmunity syndrome product, point
From more difficulty.
2) (Goossen, the Lukas J.et al.Advanced Synthesis& such as Goossen, Lukas J.
Catalysis,2009,351(16),2667-2674；Goossen,Lukas J.et al.Chemistry-A
European Journal.2009,15 (37), 9336-9349) have studied a series of with o-Carboxynitrobenzene potassium
With to halogen chlorobenzene at Hydro-Giene (Water Science). with palladium compound as catalyst, in N-Methyl pyrrolidone or its with
In the mixed solvent of luxuriant and rich with fragrance quinoline, under high temperature, reaction obtains；In the case of reaction temperature height, its by-product
More, and special reagent is difficult to buying, cost is high.
3) Caron Laurence etc. (Caron, Laurence et al.Organic Letters.2008 10 (20),
4533-4536) report Nitrobenzol and para chlorobromobenzene and the tert-butyl alcohol in sym-trimethylbenzene. under palladium catalysis
125 DEG C of reactions obtain, but its yield only has 50%；This reaction method not only yield is low, and impurity is many,
Separation is difficult to；
4) Appukkuttan Prasad etc. (Appukkuttan, Prasad et al.Synlett, 2005 (1),
127-133；) report 2-nitrobenzene boronic acid and para chlorobromobenzene at N,N-dimethylacetamide, triphenylphosphine
Palladium is that the lower 150 DEG C of microwave reactions of part weak basic condition obtain for 10 minutes.Although this reaction response time
Short, but microwave condition reaction is not suitable for industrialized production.
For the deficiency of the preparation method of existing report, need to develop a kind of novel 4'-chloro-2-nitro connection
The preparation method of benzene.
Summary of the invention
In view of this, it is contemplated that propose a kind of method preparing the chloro-2 nitro biphenyl of 4'-, to solve
Deficiency of the prior art.
For reaching above-mentioned purpose, the technical scheme is that and be achieved in that:
A kind of method preparing the chloro-2 nitro biphenyl of 4'-, including following preparation process, with o-chloronitrobenzene
Be raw material to chlorine trifluoro-benzene potassium borate, add phase transfer catalyst and palladium class catalyst, at aqueous solution
Under middle heating condition, reaction obtains the chloro-2 nitro biphenyl of 4'-, and reaction is to carry out under the conditions of weak base；Excellent
Choosing, pH is 8～10.Reaction structure formula is as follows:
Preferably, described o-chloronitrobenzene and be to the mol ratio of chlorine trifluoro-benzene potassium borate
1:(1.1～1.5).
Preferably, the mol ratio of described o-chloronitrobenzene, phase transfer catalyst and palladium class catalyst is 1:
(0.2～0.8): (0.0003～0.0009).
Preferably, described o-chloronitrobenzene is 1:(650～730 with the mol ratio of water).
Preferably, described phase transfer catalyst is tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutyl bromine
Change in ammonium or benzyltriethylammoinium chloride one or both, preferably tetrabutyl ammonium bromide.
Preferably, described palladium class catalyst is Palladous chloride., palladium or ring palladium class, preferably ring palladium class
Compound, its structure is as follows:
Ring palladium compounds of the present invention can replace part to carry out catalyzed coupling reaction, report in document
Organo-metallic catalyst market is difficult to buy, needs to synthesize in the lab, although synthesis step is more,
But operate relatively simple.Prepared by the method that the ring palladium compounds that the present invention uses is given except employing
Outside compound, it is also possible to use the compound that in existing document prepared by the additive method of report.
Preferably, described weak base condition sodium carbonate, potassium carbonate or sodium phosphate preparation, it is preferably,
Potassium carbonate, and the mol ratio of o-chloronitrobenzene and potassium carbonate is 1:(1.8～2.2).
Preferably, described heating condition refers to react at 90～100 DEG C；Preferably, reaction temperature
It it is 95～100 DEG C.
Preferably, also including filtering purification step, after stopped reaction, be down to room temperature, filter, filtrate is used
Dichloromethane extracts, and filtrate solvent evaporated adds petroleum ether and stirring 20～40min, filters, filter cake
Use dehydrated alcohol recrystallization again, obtain the chloro-2 nitro biphenyl of yellow-brown solid 4'-.
Present invention simultaneously provides a kind of method of the chloro-2 nitro biphenyl of 4'-of preparing as above in preparation pyridine
Application in acyl bacterium amine.
Relative to prior art, a kind of method preparing the chloro-2 nitro biphenyl of 4'-of the present invention, tool
There is following advantage: preparation method of the present invention, simple to operate, raw material is prone to buy and environment
Less pollution；And it is high to have yield, the advantages such as product quality is preferable.
Detailed description of the invention
Below by the embodiment under different mol ratio, the present invention will be described in more detail.Yield is to rub
You represent by percent.
Embodiment 1
By 15.7g (0.1mol) o-chloronitrobenzene, 28.4g (0.13mol) to chlorine trifluoro-benzene potassium borate, 27.6
G (0.2mol) potassium carbonate, 16.1g (0.05mol) tetrabutyl ammonium bromide joins in there-necked flask, adds 0.035
The ring palladium compound I of g (0.00006mol), (mol ratio is: adjacent chlorine nitre to add 1240mL (69mol) water
Base benzene: to chlorine trifluoro-benzene potassium borate: potassium carbonate: tetrabutyl ammonium bromide: ring palladium compound: water
=1:1.3:2:0.5:0.0006:690)；It is warming up to 100 DEG C of back flow reaction to o-chloronitrobenzene reaction completely.Stop
Only reaction, is down to room temperature.Filtering, filtrate adds 500mL dichloromethane separatory, and extraction, aqueous phase is used again
500mL dichloromethane extracts at twice, merges organic facies, and anhydrous magnesium sulfate is dried, and filters, and filtrate is steamed
Dry solvent, adds 200mL petroleum ether and stirring 30min, filters in residue, 150mL used again by filter cake
Dehydrated alcohol recrystallization, obtains yellow-brown solid i.e. 4'-chloro-2 nitro biphenyl 19.5g, yield 83.62%.
Embodiment 2
By 15.7g (0.1mol) o-chloronitrobenzene, 32.7g (0.15mol) to chlorine trifluoro-benzene potassium borate,
30.4g (0.22mol) potassium carbonate, 25.7g (0.08mol) tetrabutyl ammonium bromide joins in there-necked flask, adds
The ring palladium compound I of 0.052g (0.00009mol), addition 1310mL (73mol) water (mol ratio is:
O-chloronitrobenzene: to chlorine trifluoro-benzene potassium borate: potassium carbonate: tetrabutyl ammonium bromide: ring palladium compound: water
=1:1.5:2.2:0.8:0.0009:730)；It is warming up to 95 DEG C of back flow reaction to o-chloronitrobenzene reaction completely.Stop
Only reaction, is down to room temperature.Filtering, filtrate adds 500mL dichloromethane separatory, and extraction, aqueous phase is used again
500mL dichloromethane extracts at twice, merges organic facies, and anhydrous magnesium sulfate is dried, and filters, and filtrate is steamed
Dry solvent, adds 200mL petroleum ether and stirring 30min, filters in residue, 150mL used again by filter cake
Dehydrated alcohol recrystallization, obtains yellow-brown solid i.e. 4'-chloro-2 nitro biphenyl 19.4g, yield 83.05%.
Embodiment 3
By 15.7g (0.1mol) o-chloronitrobenzene, 28.4g (0.13mol) to chlorine trifluoro-benzene potassium borate,
26.2g (0.19mol) potassium carbonate, 19.3g (0.06mol) tetrabutyl ammonium bromide joins in there-necked flask, adds
The ring palladium compound I of 0.029g (0.00005mol), addition 1280mL (71mol) water (mol ratio is:
O-chloronitrobenzene: to chlorine trifluoro-benzene potassium borate: potassium carbonate: tetrabutyl ammonium bromide: ring palladium compound: water
=1:1.3:1.9:0.6:0.0005:710)；It is warming up to 100 DEG C of back flow reaction to o-chloronitrobenzene reaction completely.
Stopped reaction, is down to room temperature.Filtering, filtrate adds 500mL dichloromethane separatory, and extraction, aqueous phase is again
Extracting at twice with 500mL dichloromethane, merge organic facies, anhydrous magnesium sulfate is dried, and filters, filter
Liquid solvent evaporated, adds 200mL petroleum ether and stirring 30min, filters in residue, filter cake is again with 150
ML dehydrated alcohol recrystallization, obtains yellow-brown solid i.e. 4'-chloro-2 nitro biphenyl 19.26g, yield 82.47%.
In the embodiment of the present invention 1～embodiment 3, the synthetic route of the ring palladium compound of use is as follows:
Its preparation method can be carried out according to following four steps:
1) synthesis of phenylacetate
23.51g (0.25mol) phenol joins in there-necked flask, adds 26.52g (0.25mol) acetic anhydride, slow
Slowly being warming up to backflow, reaction 6h, TLC detection raw material reacts completely.Stopped reaction, stirring drops to
Room temperature, adds 100mL frozen water, continues stirring 30min.Separatory, water layer 20mL absolute ether
Extraction, organic layer is washed twice with 20mL 10% sodium hydrate aqueous solution respectively, merges organic layer, by nothing
Water magnesium sulfate is dried, sucking filtration, filtrate solvent evaporated, obtains light brown liquid phenylacetate 25.83g, yield
75.97%.
2) synthesis of parahydroxyacet-ophenone
13.60g (0.10mol) phenylacetate is dissolved in 100ml 1, in 2-dichloroethanes, stirs, slowly under room temperature
Slowly adding 15.96g (0.12mol) aluminum chloride, control temperature and be less than 60 DEG C, about 20min adds.Add
Enter in oil bath intensification, react 9h, TLC detection raw material between 60-70 DEG C and react completely.Stop stirring,
It is down to room temperature, adds 100mL water and 15mL hydrochloric acid, stir 20min, have a small amount of solid to separate out,
Sucking filtration.Filtrate air-distillation, is evaporated off water and ortho position by-product.Residue is brown solid, adds 30mL
Absolute ether, 3g activated carbon reflux decolour 30min.Sucking filtration, filtrate solvent evaporated, obtain transparent crystal
Parahydroxyacet-ophenone 8.32g, yield 61.18%.
3) synthesis of p-Hydroxyacetophenone oxime
5.01g (0.037mol) parahydroxyacet-ophenone joins in there-necked flask, adds 50mL water, and 4.29
G (0.062mol) oxammonium hydrochloride. and 6.07g (0.074mol) sodium acetate, stirring is warming up to 60 DEG C, reactant liquor
Clarification.React 8h, TLC detection raw material between 60-65 DEG C to react completely.Stop stirring, sucking filtration of lowering the temperature,
Filtrate adds 30mL dehydrated alcohol, major part alcohol-water mixture, residue cooling crystallize is evaporated off, takes out
Filter, obtains pale yellow crystals p-Hydroxyacetophenone oxime 2.55g, yield 45.64%.
4) synthesis of ring palladium compound
0.0023g (0.15mmol) p-Hydroxyacetophenone oxime joins in four-hole bottle, adds 0.05g (0.15
Mmol) K2PdCl4 and 0.013g (0.15mmol) sodium acetate, adds 15mL absolute methanol, under room temperature
Stirring reaction 2d.Reactant liquor is evaporated methanol and obtains yellow thick liquid, add 5mL water, have solid to analyse
Go out, sucking filtration, obtain brown solid ring palladium compound 0.032g, yield 59.26%.
The foregoing is only the preferred embodiment of the invention, not in order to limit present invention wound
Make, within all spirit in the invention and principle, any modification, equivalent substitution and improvement made
Deng, within should be included in the protection domain of the invention.
Claims (10)
1. the method preparing the chloro-2 nitro biphenyl of 4'-, it is characterised in that: include following preparation process,
With o-chloronitrobenzene and to chlorine trifluoro-benzene potassium borate as raw material, add phase transfer catalyst and palladium class catalysis
Agent, under heating condition, reaction obtains the chloro-2 nitro biphenyl of 4'-in aqueous, and reaction is at weak base bar
Carry out under part；Preferably, pH is 8～10.
The method preparing the chloro-2 nitro biphenyl of 4'-the most according to claim 1, it is characterised in that:
Described o-chloronitrobenzene and the mol ratio to chlorine trifluoro-benzene potassium borate are 1:(1.1～1.5).
The method preparing the chloro-2 nitro biphenyl of 4'-the most according to claim 1 and 2, its feature exists
In: the mol ratio of described o-chloronitrobenzene, phase transfer catalyst and palladium class catalyst is 1:(0.2～0.8):
(0.0003～0.0009).
The method preparing the chloro-2 nitro biphenyl of 4'-the most according to claim 3, it is characterised in that:
Described o-chloronitrobenzene is 1:(650～730 with the mol ratio of water).
The method preparing the chloro-2 nitro biphenyl of 4'-the most according to claim 1 and 2, its feature exists
In: described phase transfer catalyst is tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutyl ammonium bromide or benzyl
One or both in TEBA, it is preferred that tetrabutyl ammonium bromide.
The method preparing the chloro-2 nitro biphenyl of 4'-the most according to claim 1 and 2, its feature exists
In: described palladium class catalyst is Palladous chloride., palladium or ring palladium class, preferably ring palladium compounds, its
Structure is as follows:
The method preparing the chloro-2 nitro biphenyl of 4'-the most according to claim 1 and 2, its feature exists
In: described weak base condition sodium carbonate, potassium carbonate or sodium phosphate preparation, it is preferably, potassium carbonate,
And the mol ratio of o-chloronitrobenzene and potassium carbonate is 1:(1.8～2.2).
The method preparing the chloro-2 nitro biphenyl of 4'-the most according to claim 1 and 2, its feature exists
In: described heating condition refers to react at 90～100 DEG C；Preferably, reaction temperature is 95～100
℃。
The method preparing the chloro-2 nitro biphenyl of 4'-the most according to claim 1 and 2, its feature exists
In: also include filtering purification step, after stopped reaction, be down to room temperature, filter, filtrate dichloromethane
Extraction, filtrate solvent evaporated, add petroleum ether and stirring 20～40min, filter, filter cake is again with anhydrous
Ethyl alcohol recrystallization, obtains the chloro-2 nitro biphenyl of yellow-brown solid 4'-.
10. prepare according to the method preparing the chloro-2 nitro biphenyl of 4'-described in any one of claim 1～9
The application in preparing Boscalid of the 4'-chloro-2 nitro biphenyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610172604.3A CN105732392A (en) | 2016-03-23 | 2016-03-23 | Method for preparing 4'-chloro-2-nitrobiphenyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610172604.3A CN105732392A (en) | 2016-03-23 | 2016-03-23 | Method for preparing 4'-chloro-2-nitrobiphenyl |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105732392A true CN105732392A (en) | 2016-07-06 |
Family
ID=56251413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610172604.3A Pending CN105732392A (en) | 2016-03-23 | 2016-03-23 | Method for preparing 4'-chloro-2-nitrobiphenyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105732392A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109956871A (en) * | 2017-12-25 | 2019-07-02 | 浙江省化工研究院有限公司 | A kind of preparation method of the fluoro- 2 '-nitrobiphenyl of 3,4,5- tri- |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163452A (en) * | 1996-03-25 | 1997-10-29 | 株式会社东芝 | Optical disc device and replacing processing method |
| CN1163452C (en) * | 1996-03-13 | 2004-08-25 | 巴斯福股份公司 | Process for preparing nitrobiphenylene |
| CN104230719A (en) * | 2013-06-08 | 2014-12-24 | 华中师范大学 | Method for preparing substituted biphenyl |
| CN104478797A (en) * | 2014-12-09 | 2015-04-01 | 苏州至善化学有限公司 | Preparation method of nicotinamide fungicide namely boscalid |
| CN104529794A (en) * | 2014-12-26 | 2015-04-22 | 京博农化科技股份有限公司 | Method for preparing boscalid intermediate 2-(4-chlorophenyl) aniline |
| CN104725303A (en) * | 2015-02-02 | 2015-06-24 | 西安近代化学研究所 | Synthetic method of 2-chloro-N-(4'-chlorodiphenyl-2-yl) nicotinamide |
-
2016
- 2016-03-23 CN CN201610172604.3A patent/CN105732392A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163452C (en) * | 1996-03-13 | 2004-08-25 | 巴斯福股份公司 | Process for preparing nitrobiphenylene |
| CN1163452A (en) * | 1996-03-25 | 1997-10-29 | 株式会社东芝 | Optical disc device and replacing processing method |
| CN104230719A (en) * | 2013-06-08 | 2014-12-24 | 华中师范大学 | Method for preparing substituted biphenyl |
| CN104478797A (en) * | 2014-12-09 | 2015-04-01 | 苏州至善化学有限公司 | Preparation method of nicotinamide fungicide namely boscalid |
| CN104529794A (en) * | 2014-12-26 | 2015-04-22 | 京博农化科技股份有限公司 | Method for preparing boscalid intermediate 2-(4-chlorophenyl) aniline |
| CN104725303A (en) * | 2015-02-02 | 2015-06-24 | 西安近代化学研究所 | Synthetic method of 2-chloro-N-(4'-chlorodiphenyl-2-yl) nicotinamide |
Non-Patent Citations (1)
| Title |
|---|
| EMILIO ALACID等: "First Cross-Coupling Reaction of Potassium Aryltrifluoroborates with Organic Chlorides in Aqueous Media Catalyzed by an Oxime-Derived Palladacycle，Emilio Alacid and Carmen Na´jera", 《ORG. LETT.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109956871A (en) * | 2017-12-25 | 2019-07-02 | 浙江省化工研究院有限公司 | A kind of preparation method of the fluoro- 2 '-nitrobiphenyl of 3,4,5- tri- |
| CN109956871B (en) * | 2017-12-25 | 2022-03-29 | 浙江省化工研究院有限公司 | Preparation method of 3,4, 5-trifluoro-2' -nitrobiphenyl |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1760057A1 (en) | Method for producing polyhalogenated diamantane and derivative thereof | |
| CN101823952A (en) | Method for preparing 2,4,5-trifluorophenylacetic acid | |
| CN103641722A (en) | Production method for 2-nitrobenzyl bromide | |
| CN101757950A (en) | Catalyst system and application for leading poly-fluorine phenyl in organic synthesis thereof | |
| CN103172480B (en) | Method for preparing iodo aromatic hydrocarbon | |
| CN107445795A (en) | A kind of synthetic method of the aryl building block of the fluoro ethyl of 2 bromine 1,1,2,2 four substitution | |
| CN103193608A (en) | Method for preparing dimethoxy benzaldehyde from veratrole | |
| CN105732392A (en) | Method for preparing 4'-chloro-2-nitrobiphenyl | |
| CN102863399B (en) | Synthetic method for isatoic anhydride derivative | |
| CN104447336B (en) | A kind of three dish ene derivatives and preparation method thereof | |
| CN110950778A (en) | Process and catalyst system for preparing aromatic malononitrile | |
| CN107011288B (en) | A kind of preparation method of aripiprazole intermediate 1- (2,3- dichlorophenyl) piperazine hydrochloride | |
| CN103922904B (en) | A kind of method of synthetic 2-fluorinated aryl carbonyls | |
| CN104803829B (en) | A kind of method of asymmetric syntheses chirality diarylcarbinols | |
| CN107915694A (en) | 1 [2 (2,4 3,5-dimethylphenyl sulfydryl) phenyl] piperazine hydrochloride and preparation method thereof | |
| CN103880573A (en) | Preparation method for biphenyl-type compound | |
| CN102675148A (en) | Preparation method of hydroxybenzyl cyanide | |
| CN106916094B (en) | A kind of preparation method of indole dione compound | |
| CN105944762A (en) | Phenanthroline copper complex catalyst, preparation method and application thereof | |
| CN105254485B (en) | A kind of method of o-phenylenediamine condensing benzaldehyde Bis-Schiff Bases palladium complex catalyst synthesis difunisal | |
| CN109422681A (en) | A kind of preparation method of Pitavastatin Calcium intermediate | |
| CN104876861A (en) | Method for producing 2-chloro nicotinic acid | |
| CN103524313A (en) | 3,5-dimethylbenzaldehyde preparation method | |
| CN102285878B (en) | Method for preparing 2-halo-4,5-dimethoxy benzoic acid | |
| CN109704987B (en) | Method for synthesizing 2-fluorobenzene amine compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160706 |
|
| RJ01 | Rejection of invention patent application after publication |