CN103772151A - Preparation method of 2-methyl-3-phenyl benzyl alcohol - Google Patents
Preparation method of 2-methyl-3-phenyl benzyl alcohol Download PDFInfo
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- CN103772151A CN103772151A CN201410053397.0A CN201410053397A CN103772151A CN 103772151 A CN103772151 A CN 103772151A CN 201410053397 A CN201410053397 A CN 201410053397A CN 103772151 A CN103772151 A CN 103772151A
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- dimethyl diphenyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- -1 2-methyl-3-phenyl benzyl Chemical group 0.000 title claims abstract description 14
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title abstract 4
- 235000019445 benzyl alcohol Nutrition 0.000 title abstract 2
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000005886 esterification reaction Methods 0.000 claims abstract description 20
- NBYFWZAXXNLBEG-UHFFFAOYSA-N 1-(chloromethyl)-2-methyl-3-phenylbenzene Chemical group CC1=C(CCl)C=CC=C1C1=CC=CC=C1 NBYFWZAXXNLBEG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000032050 esterification Effects 0.000 claims abstract description 19
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 239000004305 biphenyl Substances 0.000 claims description 61
- 235000010290 biphenyl Nutrition 0.000 claims description 61
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- RIGLZCCHIBMOIN-UHFFFAOYSA-N 1-(2-methyl-3-phenylphenyl)-2-phenylethane-1,2-dione Chemical compound CC1=C(C=CC=C1C1=CC=CC=C1)C(=O)C(=O)C1=CC=CC=C1 RIGLZCCHIBMOIN-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000005286 illumination Methods 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 21
- 229910052801 chlorine Inorganic materials 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 10
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical group [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000006298 dechlorination reaction Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 239000003039 volatile agent Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012264 purified product Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 4
- GYDBFRBGTUUSBC-UHFFFAOYSA-N 2,2-dimethylpropanoic acid;sodium Chemical compound [Na].CC(C)(C)C(O)=O GYDBFRBGTUUSBC-UHFFFAOYSA-N 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical group ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 3
- HCAHMRPMYBVHGU-UHFFFAOYSA-N 1,2-dimethyl-3-phenylbenzene Chemical group CC1=CC=CC(C=2C=CC=CC=2)=C1C HCAHMRPMYBVHGU-UHFFFAOYSA-N 0.000 abstract 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 238000001514 detection method Methods 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- CRDHZEIXDLOKDC-UHFFFAOYSA-N DMBP Natural products N(C1=CC=C(C(=O)C2=CC=C(NC)C=C2)C=C1)(C)C CRDHZEIXDLOKDC-UHFFFAOYSA-N 0.000 description 7
- RFVHVYKVRGKLNK-UHFFFAOYSA-N bis(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1 RFVHVYKVRGKLNK-UHFFFAOYSA-N 0.000 description 7
- RZTDESRVPFKCBH-UHFFFAOYSA-N p-Tol-Tol-p Natural products C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000003747 Grignard reaction Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000013517 stratification Methods 0.000 description 3
- JNXJARJANRFDKX-UHFFFAOYSA-N 1-chloro-2-methyl-3-phenylbenzene Chemical group CC1=C(Cl)C=CC=C1C1=CC=CC=C1 JNXJARJANRFDKX-UHFFFAOYSA-N 0.000 description 2
- ZUVPLKVDZNDZCM-UHFFFAOYSA-N 3-chloro-2-methylaniline Chemical compound CC1=C(N)C=CC=C1Cl ZUVPLKVDZNDZCM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000005874 Bifenthrin Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- OMFRMAHOUUJSGP-IRHGGOMRSA-N bifenthrin Chemical compound C1=CC=C(C=2C=CC=CC=2)C(C)=C1COC(=O)[C@@H]1[C@H](\C=C(/Cl)C(F)(F)F)C1(C)C OMFRMAHOUUJSGP-IRHGGOMRSA-N 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
- C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 2-methyl-3-phenyl benzyl alcohol. The preparation method comprises the steps of (1) under a lighting condition, enabling 2,3-dimethyl biphenyl to mix and react with chlorine gas at 40-120 DEGC; or, in the presence of an initiator, enabling the 2,3-dimethyl biphenyl to react with sulfuryl chloride or chlorine gas at 40-120 DEG C; (2) implementing an esterification reaction on 2-methyl-3-chloromethyl biphenyl prepared by the step (1) and an esterification reagent in a solvent in the presence of a catalyst; and (3) under an alkaline condition, hydrolyzing an esterification product prepared by the step (2), and controlling pH range within 9-14. The preparation method disclosed by the invention is simple and convenient to operate, relatively low in cost, not high in requirement on equipment and applicable to industrial production. (img file='DDA0000466672690000011. TIF'wi='1528'he='344'/).
Description
Technical field
The present invention relates to a kind of preparation method of 2-methyl-3-phenyl benzil alcohol.
Background technology
2-methyl-3-phenyl benzil alcohol is an important intermediate producing agricultural chemicals bifenthrin and other agricultural chemicals medicine.
The method of preparing at present 2-methyl-3-phenyl benzil alcohol mainly contains four kinds:
First method is with 2,6-toluene dichloride is raw material, THF is solvent, after a step grignard reaction, reacts make 3-chloro-2-methyl biphenyl with bromobenzene under catalyzer, then in THF, carries out obtaining target product with formaldehyde gas or paraformaldehyde direct reaction after second step grignard reaction.
Second method (CN1935761A, CN101130485A) be with 2,6-toluene dichloride is raw material, THF is solvent, after a step grignard reaction, react under catalyzer with bromobenzene and make 3-chloro-2-methyl biphenyl, then in THF, carry out directly reacting generation 2-methyl-3-phenyl phenyl aldehyde with DMF after second step grignard reaction, then obtain target product with NaBH4 or the reduction of other metallic reducing agent.
The third method (CN101704723A) is take 2-methyl-3-chloroaniline as raw material, under the existence of metal catalyst, acids promotor and nitrous acid ester, carrying out diazonium coupling with benzene reacts and makes 2-methyl-3-chlordiphenyl, carry out again grignard reaction, carbonyl addition makes 2-methyl-3-phenyl phenyl aldehyde, finally under metallic reducing agent reduction, obtain.
The 4th kind of method (CN102603485A) is take the bromo-2-tolyl acid of 3-as raw material, under palladium-containing catalyst catalysis, there is Suzuki linked reaction with phenyl substituted boracic acid/phenyl substituted boracic acid salt and make 3-phenyl-2-tolyl acid, then obtain target product through reduction.
But method one, method two and method three have all been applied to grignard reaction, need anhydrous and oxygen-free operation, and equipment cost is higher.Method two, three, four need use the carbonyl reduction agent that price is more expensive, and cost is higher.
Summary of the invention
Technical problem to be solved by this invention is, in order to overcome, preparation method's cost of 2-methyl-3-phenyl benzil alcohol in prior art is higher, complex operation, higher to equipment requirements, be unfavorable for the defects such as suitability for industrialized production, and a kind of preparation method of 2-methyl-3-phenyl benzil alcohol is provided.Preparation method of the present invention is easy and simple to handle, cost is lower, and less demanding for equipment is applicable to the needs of suitability for industrialized production.
The preparation method who the invention provides a kind of 2-methyl-3-phenyl benzil alcohol, it comprises the steps:
Step (1): under illumination condition, by 2,3-dimethyl diphenyl (DMBP) and chlorine hybrid reaction, temperature of reaction is 40 ℃～120 ℃;
Or, under initiator condition, by 2,3-dimethyl diphenyl (DMBP), to react with SULPHURYL CHLORIDE or chlorine, temperature of reaction is 40 ℃～120 ℃;
Step (2): in solvent, under catalyzer condition, 2-methyl-3-chloromethyl biphenyl (MCMBP) that step (1) is prepared carries out esterification with esterifying reagent;
Step (3): under alkaline condition, the esterification products that step (2) is prepared is hydrolyzed, controlling pH scope is 9～14;
In step (1), the reaction under illumination condition, preferably includes following steps: 2,3-dimethyl diphenyl is warming up to 40 ℃～120 ℃, opens illumination, pass into chlorine and react.
In step (1), described illumination condition, without particular requirement, can be illumination condition conventional in this area, for example, adopts electricity-saving lamp, and ultraviolet lamp or high voltage mercury lamp carry out illumination.
In step (1), the reaction under illumination condition or the reaction under initiator condition can be carried out in solvent, also can under condition of no solvent, carry out, preferably condition of no solvent.Described solvent can be the conventional organic solvent in this area.One or more in the preferred benzene of described organic solvent, chlorobenzene, phenyl polychloride, tetracol phenixin and 1,2-ethylene dichloride.The consumption of described solvent is generally the carrying out that does not affect reaction, preferably 1.0mL/g2,3-dimethyl diphenyl.
In step (1), the reaction under illumination condition, can also add catalyzer and/or initiator.The preferred phosphorus trichloride of described catalyzer or phosphorus pentachloride.The mole dosage of described catalyzer is preferably 0.5%～3% of 2,3-dimethyl diphenyl.
In step (1), the preferred Diisopropyl azodicarboxylate of described initiator or benzoyl peroxide.The mole dosage of described initiator is preferably 0.3%～1% of 2,3-dimethyl diphenyl.
In step (1), in the time that catalyzer and/or initiator are also added in the reaction under illumination condition, described reaction preferably includes following steps: by 2,3-dimethyl diphenyl, mixes with catalyzer and/or initiator, in the time of 40 ℃～120 ℃, open illumination, pass into chlorine or drip SULPHURYL CHLORIDE and react.
In step (1), only the reaction under initiator condition preferably includes following steps: 2,3-dimethyl diphenyl is mixed with initiator, in the time of 40 ℃～120 ℃, drip SULPHURYL CHLORIDE or pass into chlorine reaction.Described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; The mole dosage of described initiator is 0.3%～1% of 2,3-dimethyl diphenyl.
In step (1), preferably 80 ℃～100 ℃ of described temperature of reaction.
In step (1), the only reaction under initiator condition, the molar ratio of described SULPHURYL CHLORIDE and 2,3-dimethyl diphenyl preferably 0.7～0.9.
In step (1), the process of described reaction can be monitored by GC or HPLC, generally with vapor detection 2, the transformation efficiency of 3-dimethyl diphenyl reaches 70%(mass percent), or HPLC detects 2,3-dimethyl diphenyl transformation efficiency reaches 70%(mass percent) time, as the terminal of reaction, preferably 2 hours.
In step (1), the reaction under illumination condition, after reaction finishes, also can be further purified product by aftertreatment.Described aftertreatment preferably includes following steps: stop passing into chlorine, blast nitrogen, reaction solution rectification under vacuum, collects after cut.
In step (1), the only reaction under initiator condition, after reaction finishes, also can be further purified product by aftertreatment.Described aftertreatment preferably includes following steps: cooling reaction solution to 0 ℃, drips NaHCO under ice bath
3the aqueous solution, extraction, organic phase rectification under vacuum, collects after cut.Described NaHCO
3the NaHCO that aqueous solution preferred mass concentration is 20%
3the aqueous solution.
In step (1), the front-end volatiles that reclaim by rectification under vacuum in aftertreatment be unreacted complete 2,3-dimethyl diphenyl, recyclable applying mechanically; Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), can be used for reduction dechlorination, further prepares raw material 2,3-dimethyl diphenyl.
In step (2), described solvent can be solvent conventional in this area, preferably one or more in toluene, dimethylbenzene, dioxane and water, more preferably water.The consumption of described solvent does not generally affect the carrying out of reaction, preferably 1.0mL/g2-methyl-3-chloromethyl biphenyl.
In step (2), the preferred quaternary ammonium salt of described catalyzer.The preferred tetrabutylammonium chloride of described quaternary ammonium salt, Tetrabutyl amonium bromide, tetrabutyl ammonium fluoride or benzyl trimethyl ammonium chloride, preferably tetrabutylammonium chloride.The mole dosage of described catalyzer is preferably 0.5%～5% of 2-methyl-3-chloromethyl biphenyl.
In step (2), the preferred sodium acetate of described esterifying reagent, sodium formiate, trimethylacetic acid sodium or Sodium Benzoate, preferably sodium acetate.The molar ratio of described esterifying reagent and 2-methyl-3-chloromethyl biphenyl preferably 1.0～3.0, more preferably 1.3～1.8.
In step (2), preferably 60 ℃～120 ℃ of the temperature of reaction of described esterification, more preferably 80 ℃～100 ℃.
In step (2), institute's first is stated the reaction process of esterification and can be monitored by GC, HPLC or TLC, generally when in vapor detection reaction system, 2-base-3-chloromethyl biphenyl content is less than 1%, as the terminal of reaction, the present invention preferably 15 hours.
In the present invention, preferably, after the described esterification of step (2) finishes, directly under alkaline condition, carry out the described hydrolysis reaction of step (3) without aftertreatment; Preferably include following steps: under catalyzer condition, 2-methyl-3-chloromethyl biphenyl is mixed with esterifying reagent, carry out esterification, and then drip aqueous sodium hydroxide solution in reaction solution, be hydrolyzed, the scope of controlling pH value when hydrolysis is 9～14.
In step (3), described alkaline condition preferably adopts the NaOH aqueous solution.The mass concentration of the described NaOH aqueous solution preferably 30%.
In step (3), described pH scope preferably 10～12.
In step (3), preferably 80 ℃～100 ℃ of the temperature of reaction of described hydrolysis.
In step (3), the process of described hydrolysis can be monitored by GC, HPLC or TLC, while generally disappearance with esterification products, as the terminal of reaction, preferably 10～15 hours.
In step (3), after described hydrolysis finishes, can also further pass through aftertreatment purified product.Described aftertreatment preferably includes following steps: separatory, first alcohol and water recrystallization for organic layer, vacuum drying.The water layer that separatory obtains can recovery in the esterification of next batch.
In the preparation method of described 2-methyl-3-phenyl benzil alcohol, described 2,3-dimethyl diphenyl can make by the following method: in solvent, 2-chloromethyl-3-methyl diphenyl (CMMBP) and reductive agent are carried out to reduction dechlorination and react;
In preparation 2, in the method for 3-dimethyl diphenyl, described solvent can be the common solvent of this area, one or more in particular methanol, ethanol, tetrahydrofuran (THF), 2-methyltetrahydrofuran, dioxane, ethyl acetate and acetone, more preferably ethanol and/or tetrahydrofuran (THF).The consumption of described solvent does not generally affect the carrying out of reaction, preferably 1.0mL/g2-chloromethyl-3-methyl diphenyl.
In the method for preparation 2,3-dimethyl diphenyl, the preferred zinc powder of described reductive agent and acetic acid combination, iron powder and acetic acid combination, palladium carbon and H
2combination, platinum carbon and H
2combination, Raney's nickel and H
2combination, preferably palladium carbon and H
2combination.Hydrogen in described reductive agent or acetic acid, with the molar ratio of 2-chloromethyl-3-methyl diphenyl preferably 1.0～3.0, more preferably 1～2.0.Preferably 0.1%～5%2-chloromethyl-3-methyl diphenyl of the mole dosage of zinc powder, iron powder, palladium carbon, platinum carbon or Raney's nickel in described reductive agent, more preferably scope is 1%～5%2-chloromethyl-3-methyl diphenyl.
In the method for preparation 2,3-dimethyl diphenyl, in the time that reductive agent comprises hydrogen, preferably 0.1～0.6MPa of described hydrogen pressure, more preferably 0.1Mpa.
In the method for preparation 2,3-dimethyl diphenyl, preferably 25 ℃～80 ℃ of the temperature of described reduction dechlorination reaction, more preferably 30 ℃～70 ℃.
In the method for preparation 2,3-dimethyl diphenyl, can also further add acid binding agent.The preferred sodium carbonate of described acid binding agent.The consumption of described acid binding agent is preferably 1.1～2.0 times of 2-chloromethyl-3-methyl diphenyl molar weight.
In the method for preparation 2,3-dimethyl diphenyl, the process of described reduction dechlorination reaction can be monitored by GC, HPLC or TLC, while generally disappearance with 2-chloromethyl-3-methyl diphenyl, as the terminal of reaction, preferably 6～63 hours, more preferably 10～48 hours.
After described reduction dechlorination reaction finishes, also can be further purified product by aftertreatment.Described aftertreatment preferably includes following steps: filters, and except desolventizing, resistates underpressure distillation.
Above-mentioned preparation 2, in the method for 3-dimethyl diphenyl, raw material 2-chloromethyl-3-methyl diphenyl (CMMBP) used can be taken from the by product that 2,3-dimethyl diphenyl obtains after according to above-mentioned chlorination reaction.
Therefore,, in the present invention, an operational path of preferably preparing 2-methyl-3-phenyl benzil alcohol is:
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is: 2-methyl-3-phenyl benzil alcohol preparation method of the present invention, greatly reduce raw materials cost, and reduce the requirement to equipment, simple to operate, be suitable for suitability for industrialized production.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to ordinary method and condition, or selects according to catalogue.
Embodiment 1
In 500mL four-hole bottle, add 182.3g2,3-dimethyl diphenyl (DMBP), is warming up to after 80 degree, open illumination, start to pass into chlorine, temperature is controlled in 100 ℃, after vapor detection transformation efficiency approximately 70%, stop logical chlorine and blast nitrogen, take away remaining chlorine and hydrogenchloride.Reaction solution underpressure distillation.Front-end volatiles 51.9g, for unreacted complete 2,3-dimethyl diphenyl, yield 28.5%.Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), 82.6g, and yield 38.1%, can be used for preparing the reaction of 2,3-dimethyl diphenyl.After cut is mainly 2-methyl-3-chloromethyl biphenyl (MCMBP), 62.8g, and yield 29.0%, can be used for follow-up preparation 2-methyl-3-phenyl benzil alcohol reaction.
Embodiment 2
In four-hole bottle, add 182.3g2,3-dimethyl diphenyl (DMBP), 4.2g phosphorus pentachloride, be warming up to after 80 ℃, open illumination, start to pass into chlorine, control temperature and be less than 100 ℃, after vapor detection transformation efficiency approximately 70%, under ice bath, slowly drip the NaHCO of 42.0g20%
3solution.Extracting and demixing, organic phase underpressure distillation.Front-end volatiles 53.8g, for unreacted complete 2,3-dimethyl diphenyl, yield 29.5%.Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), 84.3g, and yield 38.9%, for the preparation of the reaction of 2,3-dimethyl diphenyl.After cut is mainly 2-methyl-3-chloromethyl biphenyl (MCMBP), 64.1g, and yield 29.6%, can be used for follow-up preparation 2-methyl-3-phenyl benzil alcohol reaction.
Embodiment 3
In four-hole bottle, add 182.3g2,3-dimethyl diphenyl (DMBP), 4.2g phosphorus pentachloride, is warming up to after 40 ℃, opens illumination, starts to pass into chlorine, after vapor detection transformation efficiency approximately 70%, slowly drips the NaHCO3 solution of 42.0g20% under ice bath.Extracting and demixing, organic phase underpressure distillation.Front-end volatiles 56.5g, for unreacted complete 2,3-dimethyl diphenyl, yield 31.0%.Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), 80.2g, and yield 37.0%, for the preparation of the reaction of 2,3-dimethyl diphenyl.After cut is mainly 2-methyl-3-chloromethyl biphenyl (MCMBP), 57.2g, and yield 26.4%, can be used for follow-up preparation 2-methyl-3-phenyl benzil alcohol reaction.
Embodiment 4
In four-hole bottle, add 182.3g2,3-dimethyl diphenyl (DMBP), 1.6g Diisopropyl azodicarboxylate, is warming up to after 80 ℃, opens illumination, start to pass into chlorine, temperature is controlled in 100 ℃, after vapor detection transformation efficiency approximately 70%, stops logical chlorine, blast nitrogen, to take away remaining chlorine and hydrogenchloride.Reaction solution underpressure distillation.Front-end volatiles be unreacted complete 2,3-dimethyl diphenyl, 47.8g, yield 26.2%, recovery.Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), 81.3g, and yield 37.5%, for the preparation of the reaction of 2,3-dimethyl diphenyl.After cut is 2-methyl-3-chloromethyl biphenyl (MCMBP), 60.7g, and yield 28.0%, can be used for the reaction of 2-methyl-3-phenyl benzil alcohol.
Embodiment 5
In four-hole bottle, add 182.3g2,3-dimethyl diphenyl (DMBP), 3.3g Diisopropyl azodicarboxylate, be warming up to after 80 ℃, in 3 hours, slowly drip 108.0g SULPHURYL CHLORIDE, dropwise rear 80 ℃ of insulations 2 hours, after be cooled to 0 ℃, under ice bath, slowly drip the NaHCO of 84.0g20%
3solution.Extracting and demixing, organic phase underpressure distillation.Front-end volatiles 31.3g, for unreacted complete 2,3-dimethyl diphenyl, yield 17.2%.Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), 105.3g, and yield 48.6%, for the preparation of the reaction of 2,3-dimethyl diphenyl.After cut is mainly 2-methyl-3-chloromethyl biphenyl (MCMBP), 67.4g, and yield 31.1%, can be used for preparing the reaction of 2-methyl-3-phenyl benzil alcohol.
Embodiment 6
In four-hole bottle, add 2-chloromethyl-3-methyl diphenyl (CMMBP) 86.7g, 110.6g ethanol, 48.0g acetic acid, is cooled to after 25 ℃, in 6 hours, adds 31.4g zinc powder in batches.After zinc powder adds, 25 ℃ are incubated 48 hours, steam ethanol and unreacted acetic acid, recovery after middle control is qualified.The residual water that adds of still, extraction, organic phase decompression precipitation, reclaims 2,3-dimethyl diphenyl 69.6g, and yield 95.5% can return and apply mechanically preparation 2-methyl-3-chloromethyl biphenyl.
Embodiment 7
In four-hole bottle, add 2-chloromethyl-3-methyl diphenyl (CMMBP) 86.7g, 86.5g tetrahydrofuran (THF), 48.0g acetic acid, is cooled to after 25 ℃, in 6 hours, adds 31.4g zinc powder in batches.After zinc powder adds, 25 ℃ are incubated 63 hours, steam tetrahydrofuran (THF) and unreacted acetic acid, recovery after middle control is qualified.The residual water that adds of still, extraction, organic phase decompression precipitation, reclaims 2,3-dimethyl diphenyl 67.8g, and yield 93.0% can return and apply mechanically preparation 2-methyl-3-chloromethyl biphenyl.
Embodiment 8
In 500mL autoclave, add 2-chloromethyl-3-methyl diphenyl (CMMBP) 86.7g, 92.1g ethanol, 2.6g5%Pd/C, 63.6g Na
2cO
3, with the hydrogen that is filled with 0.1MPa after hydrogen exchange three times, be warming up to 50 ℃ of insulation 6h.Filter, reclaim catalyzer, steam ethanol, recovery.Mother liquor underpressure distillation, obtains 2,3-dimethyl diphenyl 71.2g, and yield 97.6% can return and apply mechanically preparation 2-methyl-3-chloromethyl biphenyl.
Embodiment 9
In 500mL autoclave, add 2-chloromethyl-3-methyl diphenyl (CMMBP) 86.7g, 92.1g ethanol, 63.6g Na
2cO
3, 0.9g Raney's nickel, with the hydrogen that is filled with 0.6MPa after hydrogen exchange three times, is warming up to 70 ℃ of insulation 10h.Filter, mother liquor normal pressure steams ethanol, and rear underpressure distillation obtains 2,3-dimethyl diphenyl 66.6g, and yield 91.4% can return and apply mechanically preparation 2-methyl-3-chloromethyl biphenyl.
Embodiment 10
In four-hole bottle, add 65.0g2-methyl-3-chloromethyl biphenyl (MCMBP), 2.5g tetrabutylammonium chloride, 73.8g50% aqueous sodium acetate solution, be warming up to backflow, 100 ℃ of insulations 15 hours, after vapor detection raw material is less than 1%, to the NaOH aqueous solution that slowly drips 44.0g30% in reaction solution, control pH between 9-10,100 ℃ insulation 10 hours after, 60 ℃ of stratification, mother liquor recovery, toluene and mixed heptane recrystallization for organic layer, obtain BFA wet product.Crude product vacuum drying obtains the finished product BFA52.3g, and purity is greater than 99.8%(GC), yield 88.0%.
Embodiment 11
In four-hole bottle, add 65.0g2-methyl-3-chloromethyl biphenyl (MCMBP), 2.5g tetrabutylammonium chloride, 89.4g50% trimethylacetic acid sodium water solution, be warming up to backflow, 100 ℃ of insulations 15 hours, after vapor detection raw material is less than 1%, to the NaOH aqueous solution that slowly drips 44.0g30% in reaction solution, control pH between 9-10,100 ℃ insulation 15 hours after, 60 ℃ of stratification, mother liquor recovery, first alcohol and water recrystallization for organic layer, obtains BFA wet product.Crude product vacuum drying obtains the finished product BFA48.9g, and purity is greater than 99.0%(GC), yield 82.2%.
Embodiment 12
In four-hole bottle, add 65.0g2-methyl-3-chloromethyl biphenyl (MCMBP), 2.9g tetra-n-butyl ammonium bromide, 73.8g50% aqueous sodium acetate solution, be warming up to backflow, 100 ℃ of insulations 15 hours, after vapor detection raw material is less than 1%, to the NaOH aqueous solution that slowly drips 44.0g30% in reaction solution, control pH between 12-13,100 ℃ insulation 10 hours after, 60 ℃ of stratification, mother liquor recovery, toluene and mixed heptane recrystallization for organic layer, obtain BFA wet product.Crude product vacuum drying obtains the finished product BFA54.1g, and purity is greater than 99.5%(GC), yield 91.0%.
Claims (15)
1. a preparation method for 2-methyl-3-phenyl benzil alcohol, it comprises the steps:
Step (1): under illumination condition, by 2,3-dimethyl diphenyl and chlorine hybrid reaction, temperature of reaction is 40 ℃～120 ℃;
Or, under initiator condition, by 2,3-dimethyl diphenyl, to react with SULPHURYL CHLORIDE or chlorine, temperature of reaction is 40 ℃～120 ℃;
Step (2): in solvent, under catalyzer condition, 2-methyl-3-chloromethyl biphenyl and esterifying reagent that step (1) is prepared carry out esterification;
Step (3): under alkaline condition, the esterification products that step (2) is prepared is hydrolyzed, controlling pH scope is 9～14;
2. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (1), and the reaction under illumination condition, comprise the steps: 2,3-dimethyl diphenyl is warming up to 40 ℃～120 ℃, opens illumination, passes into chlorine and reacts.
3. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (1), the chlorination reaction under two kinds of conditions is carried out or carried out under condition of no solvent in solvent; Described solvent is organic solvent; Described organic solvent is one or more in benzene, chlorobenzene, phenyl polychloride, tetracol phenixin and 1,2-ethylene dichloride.
4. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (1), the reaction under illumination condition, further adds catalyzer and/or initiator; Described catalyzer is phosphorus trichloride or phosphorus pentachloride; The mole dosage of described catalyzer is 0.5%～3% of 2,3-dimethyl diphenyl; Described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; The mole dosage of described initiator is 0.3%～1% of 2,3-dimethyl diphenyl.
5. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, it is characterized in that: in step (1), in the time that catalyzer and/or initiator are also added in the reaction under illumination condition, described reaction comprises the steps: 2,3-dimethyl diphenyl, mixes with catalyzer and/or initiator, in the time of 40 ℃～120 ℃, open illumination, pass into chlorine or drip SULPHURYL CHLORIDE and react.
6. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, it is characterized in that: in step (1), only the reaction under initiator condition comprises the steps: 2,3-dimethyl diphenyl mixes with initiator, in the time of 40 ℃～120 ℃, drip SULPHURYL CHLORIDE or pass into chlorine reaction; Described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; The mole dosage of described initiator is 0.3%～1% of 2,3-dimethyl diphenyl.
7. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (1), described temperature of reaction is 80 ℃～100 ℃; In step (1), the described only reaction under initiator condition, the molar ratio of described SULPHURYL CHLORIDE and 2,3-dimethyl diphenyl is 0.7～0.9.
8. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (1), the only reaction under initiator condition, after reaction finishes, is further purified product by aftertreatment; Described aftertreatment comprises the steps: cooling reaction solution to 0 ℃, under ice bath, drips NaHCO
3the aqueous solution, extraction, organic phase rectification under vacuum, collects after cut;
In step (1), the front-end volatiles that reclaim by rectification under vacuum in aftertreatment be unreacted complete 2,3-dimethyl diphenyl, recovery; Middle cut is 2-chloromethyl-3-methyl diphenyl, and reduction dechlorination, further prepares raw material 2,3-dimethyl diphenyl.
9. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (2), described solvent is one or more in toluene, dimethylbenzene, dioxane and water; In step (2), described catalyzer is quaternary ammonium salt; Described quaternary ammonium salt is tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutyl ammonium fluoride or benzyl trimethyl ammonium chloride; The mole dosage of described catalyzer is 0.5%～5% of 2-methyl-3-chloromethyl biphenyl; In step (2), described esterifying reagent is sodium acetate, sodium formiate, trimethylacetic acid sodium or Sodium Benzoate; The molar ratio of described esterifying reagent and 2-methyl-3-chloromethyl biphenyl is 1.0～3.0.
10. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (2), the temperature of reaction of described esterification is 60 ℃～120 ℃;
After the described esterification of step (2) finishes, directly under alkaline condition, carry out the described hydrolysis reaction of step (3) without aftertreatment; Comprise the steps: under catalyzer condition, 2-methyl-3-chloromethyl biphenyl is mixed with esterifying reagent, carry out esterification, and then drip aqueous sodium hydroxide solution in reaction solution, be hydrolyzed, the scope of controlling pH value when hydrolysis is 9～14.
The preparation method of 11. 2-methyl-3-phenyl benzil alcohols as claimed in claim 10, is characterized in that: in step (2), the temperature of reaction of described esterification is 80 ℃～100 ℃.
The preparation method of 12. 2-methyl-3-phenyl benzil alcohols as claimed in claim 1, is characterized in that: in step (3), described alkaline condition adopts the NaOH aqueous solution; In step (3), described pH scope is 10～12; In step (3), the temperature of reaction of described hydrolysis is 80 ℃～100 ℃;
In step (3), after described hydrolysis finishes, also further pass through aftertreatment purified product; Described aftertreatment comprises the steps: separatory, first alcohol and water recrystallization for organic layer, vacuum drying; The water layer recovery that separatory obtains is in the esterification of next batch.
The preparation method of 13. 2-methyl-3-phenyl benzil alcohols as claimed in claim 1, is characterized in that: step (1): in solvent, 2-chloromethyl-3-methyl diphenyl is carried out to reduction dechlorination with reductive agent and react, prepare 2,3-dimethyl diphenyl;
Step (2): under illumination condition, step (1) is prepared 2,3-dimethyl diphenyl and chlorine hybrid reaction, temperature of reaction is 40 ℃～120 ℃;
Or, under initiator condition, step (1) is prepared 2,3-dimethyl diphenyl, reacts with SULPHURYL CHLORIDE or chlorine, temperature of reaction is 40 ℃～120 ℃;
Step (3): in solvent, under catalyzer condition, 2-methyl-3-chloromethyl biphenyl and esterifying reagent that step (2) is prepared carry out esterification;
Step (4): under alkaline condition, the esterification products that step (3) is prepared is hydrolyzed, controlling pH scope is 9～14;
The preparation method of 14. 2-methyl-3-phenyl benzil alcohols as claimed in claim 13, it is characterized in that: in preparation 2, in the step of 3-dimethyl diphenyl, described solvent is one or more in methyl alcohol, ethanol, tetrahydrofuran (THF), 2-methyltetrahydrofuran, dioxane, ethyl acetate and acetone;
In the step of preparation 2,3-dimethyl diphenyl, described reductive agent is zinc powder and acetic acid combination, iron powder and acetic acid combination, palladium carbon and H
2combination, platinum carbon and H
2combination, Raney's nickel and H
2combination; Hydrogen in described reductive agent or acetic acid, with the molar ratio of 2-chloromethyl-3-methyl diphenyl be 1.0～3.0; The mole dosage of zinc powder, iron powder, palladium carbon, platinum carbon or Raney's nickel in described reductive agent is 0.1%～10%2-chloromethyl-3-methyl diphenyl.
The preparation method of 15. 2-methyl-3-phenyl benzil alcohols as claimed in claim 14, is characterized in that: in the step of preparation 2,3-dimethyl diphenyl, in the time that reductive agent comprises hydrogen, described hydrogen pressure is 0.1～0.6Mpa;
In the step of preparation 2,3-dimethyl diphenyl, the temperature of described reduction dechlorination reaction is 25 ℃～80 ℃;
In the step of preparation 2,3-dimethyl diphenyl, further add acid binding agent; Described acid binding agent is sodium carbonate.
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| CN109734555A (en) * | 2019-02-01 | 2019-05-10 | 武汉格源精细化学有限公司 | Preparation method of the high-purity to methylbenzyl alcohol |
| CN110922297A (en) * | 2018-09-19 | 2020-03-27 | 张家港九力新材料科技有限公司 | Method for preparing biphenyl dichlorobenzyl through photocatalytic chlorination |
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| CN101200455A (en) * | 2007-09-29 | 2008-06-18 | 王俊华 | Method for preparing sartan drug main ring 5-(4'-formyl biphenyl-2-group)-1H-tetrazole treating hypertension |
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| CN110922297A (en) * | 2018-09-19 | 2020-03-27 | 张家港九力新材料科技有限公司 | Method for preparing biphenyl dichlorobenzyl through photocatalytic chlorination |
| CN109734555A (en) * | 2019-02-01 | 2019-05-10 | 武汉格源精细化学有限公司 | Preparation method of the high-purity to methylbenzyl alcohol |
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Address after: 224600 Jiangsu Province, Yancheng City Chemical Industry Park Applicant after: JIANGSU LIANHUA TECHNOLOGY Co.,Ltd. Applicant after: LIANHE CHEMICAL TECHNOLOGY (DEZHOU) Co.,Ltd. Applicant after: LIANHE CHEMICAL TECHNOLOGY (YANCHENG) Co.,Ltd. Applicant after: LIANHE CHEMICAL TECHNOLOGY (SHANGHAI) Co.,Ltd. Address before: 224600 Jiangsu Province, Yancheng City Chemical Industry Park Applicant before: JIANGSU LIANHUA TECHNOLOGY Co.,Ltd. Applicant before: SHANDONG PINGYUAN YONGHENG CHEMICAL Co.,Ltd. Applicant before: LIANHE CHEMICAL TECHNOLOGY (YANCHENG) Co.,Ltd. Applicant before: LIANHE CHEMICAL TECHNOLOGY (SHANGHAI) Co.,Ltd. |
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Effective date of registration: 20151210 Address after: 224600 Jiangsu Province, Yancheng City Chemical Industry Park Applicant after: JIANGSU LIANHUA TECHNOLOGY Co.,Ltd. Applicant after: LIANHE CHEMICAL TECHNOLOGY (DEZHOU) Co.,Ltd. Applicant after: LIANHE CHEMICAL TECHNOLOGY (YANCHENG) Co.,Ltd. Applicant after: LIANHE CHEMICAL TECHNOLOGY (SHANGHAI) Co.,Ltd. Applicant after: HUBEI JUNTAI MEDICINE CHEMICAL CO.,LTD. Address before: 224600 Jiangsu Province, Yancheng City Chemical Industry Park Applicant before: JIANGSU LIANHUA TECHNOLOGY Co.,Ltd. Applicant before: LIANHE CHEMICAL TECHNOLOGY (DEZHOU) Co.,Ltd. Applicant before: LIANHE CHEMICAL TECHNOLOGY (YANCHENG) Co.,Ltd. Applicant before: LIANHE CHEMICAL TECHNOLOGY (SHANGHAI) Co.,Ltd. |
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