CN109574808A - A method of alcoholic compound is prepared by the non-catalytic reaction of aromatic carboxylic acid - Google Patents
A method of alcoholic compound is prepared by the non-catalytic reaction of aromatic carboxylic acid Download PDFInfo
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- CN109574808A CN109574808A CN201811585437.0A CN201811585437A CN109574808A CN 109574808 A CN109574808 A CN 109574808A CN 201811585437 A CN201811585437 A CN 201811585437A CN 109574808 A CN109574808 A CN 109574808A
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- Prior art keywords
- acid
- carboxylic acid
- aromatic carboxylic
- borine
- hydroboration
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 230000001476 alcoholic effect Effects 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 10
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910000085 borane Inorganic materials 0.000 claims abstract description 58
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000006197 hydroboration reaction Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011261 inert gas Substances 0.000 claims abstract description 21
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 13
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 13
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- ILUJQPXNXACGAN-UHFFFAOYSA-N O-methylsalicylic acid Chemical compound COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 claims abstract description 7
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000741 silica gel Substances 0.000 claims description 42
- 229910002027 silica gel Inorganic materials 0.000 claims description 42
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 claims description 7
- OFJWFSNDPCAWDK-UHFFFAOYSA-N 2-phenylbutyric acid Chemical compound CCC(C(O)=O)C1=CC=CC=C1 OFJWFSNDPCAWDK-UHFFFAOYSA-N 0.000 claims description 5
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims description 5
- WBJWXIQDBDZMAW-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(O)=CC=C21 WBJWXIQDBDZMAW-UHFFFAOYSA-N 0.000 claims description 4
- SHSGDXCJYVZFTP-UHFFFAOYSA-N 4-ethoxybenzoic acid Chemical compound CCOC1=CC=C(C(O)=O)C=C1 SHSGDXCJYVZFTP-UHFFFAOYSA-N 0.000 claims description 4
- GHICCUXQJBDNRN-UHFFFAOYSA-N 4-iodobenzoic acid Chemical compound OC(=O)C1=CC=C(I)C=C1 GHICCUXQJBDNRN-UHFFFAOYSA-N 0.000 claims description 4
- PYHXGXCGESYPCW-UHFFFAOYSA-N alpha-phenylbenzeneacetic acid Natural products C=1C=CC=CC=1C(C(=O)O)C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-N 0.000 claims description 4
- ZHQLTKAVLJKSKR-UHFFFAOYSA-N homophthalic acid Chemical compound OC(=O)CC1=CC=CC=C1C(O)=O ZHQLTKAVLJKSKR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003617 indole-3-acetic acid Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- SEENCYZQHCUTSB-UHFFFAOYSA-N 5-bromo-2-methylbenzoic acid Chemical compound CC1=CC=C(Br)C=C1C(O)=O SEENCYZQHCUTSB-UHFFFAOYSA-N 0.000 claims 2
- YKYIFUROKBDHCY-ONEGZZNKSA-N (e)-4-ethoxy-1,1,1-trifluorobut-3-en-2-one Chemical group CCO\C=C\C(=O)C(F)(F)F YKYIFUROKBDHCY-ONEGZZNKSA-N 0.000 claims 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims 1
- WWYDYZMNFQIYPT-UHFFFAOYSA-N ru78191 Chemical compound OC(=O)C(C(O)=O)C1=CC=CC=C1 WWYDYZMNFQIYPT-UHFFFAOYSA-N 0.000 claims 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract description 23
- 230000018044 dehydration Effects 0.000 abstract description 18
- 238000006297 dehydration reaction Methods 0.000 abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 102
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 95
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 54
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 description 34
- 238000005160 1H NMR spectroscopy Methods 0.000 description 34
- 239000002904 solvent Substances 0.000 description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 27
- 238000005070 sampling Methods 0.000 description 25
- 238000004440 column chromatography Methods 0.000 description 18
- 230000005311 nuclear magnetism Effects 0.000 description 18
- 239000012044 organic layer Substances 0.000 description 18
- 239000012299 nitrogen atmosphere Substances 0.000 description 17
- 229940030010 trimethoxybenzene Drugs 0.000 description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 16
- 239000003480 eluent Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 238000000926 separation method Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- -1 boric acid ester Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910010084 LiAlH4 Inorganic materials 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N N,N-Diethylethanamine Substances CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000002024 ethyl acetate extract Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/12—Radicals substituted by oxygen atoms
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods for preparing alcoholic compound by the non-catalytic reaction of aromatic carboxylic acid.In atmosphere of inert gases, pinacol borine and carboxylic acid are uniformly mixed in the reaction flask by dehydration and deoxidation processing, reaction obtained borate after 6-12 hours, was further hydrolyzed to alcohol；The carboxylic acid is benzoic acid, 4- bromobenzoic acid, 4- fluobenzoic acid, 1- naphthoic acid, O-Anisic Acid etc..Efficiently with borine hydroboration occurs for the present invention using carboxylic acid under no catalysts conditions for the first time, and hydroboration occurs and prepares borate for carbonyls and borine, is further hydrolyzed to alcohol, provides new scheme.
Description
Technical field
The present invention relates to the application fields of Green Chemistry, and in particular to aromatic carboxylic acid and boric acid under solvent-free catalysis-free agent
The method that reaction prepares alcoholic compound.
Background technique
Alcohol is many synthesis conversions, and the important component of drug and materials synthesis, organic boric acid ester can be in certain condition
Under be converted into alcohol.Synthesis for borate, the general addition reaction for passing through carbonyls and borine, carboxylic acid and aldehyde ketone nucleophilic
The difference of addition reaction activity: (1) active hydrogen of carboxylic acid is easily left away, therefore its two O are actually equivalence, so from space
From the point of view of structure, the steric hindrance of carboxyl is larger, and the presence of carboxyl hydrogen bond, keeps the cloud density of entire carbonyl larger, nucleophilic examination
Agent attack activated centre is more difficult；(2) nucleopilic reagent elder generation attack carbonyl carbon, this is related with the cloud density on carbon, density
Small first attack, such as aldehyde ketone are smaller than the cloud density of ester, amide, so activity height, meeting preferential reaction, three-dimensional effect are big
Be not easy react；(3) to see that leaving group, the leaving group of aldehyde ketone are alkyl and hydrogen when forming transition state, the two is not
It easily leaves away, so addition only occurs for aldehyde ketone, does not eliminate, be different from carboxylic acid and its derivative.In recent years, chemists
Various catalyst are developed, the hydroboration applied to carbonyls and borine.Reported on document at present about synthesis
The reduction catalysts system of borate mainly utilizes LiAlH4 and NaBH4, SmI2-H2O-Et3N and various Transition metal complexes
The carboxylic acid hydroboration of object catalyst.But these methods have the shortcomings that it is obvious: LiAlH4 and NaBH4 system safety wind
Danger is very big, and SmI2-H2O-Et3N system needs excessive many reagents, and transient metal complex system needs under high temperature and high pressure
It carries out.
Summary of the invention
Goal of the invention of the invention is to provide a kind of method for meeting green chemistry principles, in solvent-free catalysis-free agent,
Borate is generated using the Borohydride reduction pinacol borine of carboxylic acid, and then hydrolyzes and generates alcohol.This method is environmentally protective, has very well
The substrate scope of application.Aromatic carboxylic acid is typically all solid, and aromatic carboxylic acid is heterogeneous anti-with reacting for pinacol borine
It answers.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A method of alcoholic compound is prepared by the non-catalytic reaction of aromatic carboxylic acid, is included the following steps, it is solvent-free, without catalysis
Under agent, aromatic carboxylic acid and borine carry out hydroboration；Silica gel, methanol, hydrolysis system are added after hydroboration
Standby alcoholic compound.
Aromatic carboxylic acid is preparing the application in alcoholic compound as raw material with borine, and preparing alcoholic compound includes following step
Suddenly, solvent-free, without under catalyst, aromatic carboxylic acid and borine carry out hydroboration；After hydroboration be added silica gel,
Methanol, hydrolysis prepare alcoholic compound.
In the present invention, the borine is pinacol borine；The aromatic carboxylic acid is benzoic acid, 4- bromobenzoic acid, 4- fluorine
Benzoic acid, 1- naphthoic acid, O-Anisic Acid, 4- p t butylbenzoic acid, 4- ethoxybenzoic acid, 2- bromobenzoic acid, 4- iodine
Benzoic acid, 3- benzenpropanoic acid, diphenyl acetic acid, 2- phenylbutyric acid, indole-3-acetic acid, o-carboxyl phenylacetic acid or 2- methyl -5- bromine
Benzoic acid.
In the present invention, the molar ratio of the aromatic carboxylic acid and borine is 1:3~1:7；The temperature of the hydroboration
For room temperature；The time of the hydroboration is 6~12 hours.
In the present invention, the hydroboration carries out under atmosphere of inert gases；After the hydroboration ingress of air
Reaction was completed.
In the present invention, the condition of hydrolysis is to react 3h at 50 DEG C.
In the present invention, the amount ratio of aromatic carboxylic acid and silica gel, methanol is 1mmoL:2g:6mL.
It after hydrolysis, is extracted with ethyl acetate three times, merges organic layer, dry with anhydrous sodium sulfate, decompression removes
Solvent is removed, it is column chromatography eluting by silica gel (100-200 mesh), use ethyl acetate/hexane (1:5 volume ratio) mixture as washing
De- agent, obtains alcoholic compound.
Above-mentioned technical proposal can be exemplified below:
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1. the present invention for the first time it is solvent-free and without catalyst under can carry out aromatic carboxylic acid and pinacol borine hydroboration it is anti-
It answers, to develop a kind of method for preparing boron alkyl acid esters of efficient green, and then hydrolysis generates in limited conditions
Corresponding alcoholic compound.
2. the present invention can at room temperature high activity progress aromatic carboxylic acid and borine hydroboration, reaction
It carries out 6-12 hours, can reach 90% or more conversion ratio, compared with existing catalyst system, solvent and catalyst is not used just
It can achieve very high conversion ratio.
3. the hydroboration of solvent-free catalysis-free agent carboxylic acid disclosed by the invention is wide to the scope of application of substrate, it is suitable for difference
The carboxylic acid of substituting group position, different electronic effects is combined to provide more more options for the industry of borate；And reaction process
Simple controllable, high income, product postprocessing is easy, and is suitble to industrialized production.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment one: pinacol borine and benzoic acid 3:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask benzoic acid (61.1 mg, 0.5
Mmol), pinacol borine (218 μ L, 1.5 mmol) is added with liquid-transfering gun, reacts 12 hours at room temperature, reaction is removed
Glove box, sampling (with equal trimethoxy-benzene (84.15 mg, 0.5 mmol) for internal standard, are dissolved, stirring 10 with nuclear-magnetism with CDCl3
Minute), being computed 1H yield is 99%, the nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.22-7.32
(m, 5H, ArH), 4.92 (s, 2H, CH2), 1.26 (s, 36H, CH3)；1g silica gel is added into sampling residue,
Using 3mL methanol as solvent, 3h is reacted at 50 DEG C, borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate
Three times, merge organic layer, it is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, it is pure by silica gel (100-200 mesh) column chromatography
Change, uses ethyl acetate/hexane (1:5) mixture as eluant, eluent, obtain pure primary alconol, separation yield is 92%.The nuclear-magnetism of product
Data: 1H NMR (400 MHz, CDCl3): δ 7.22-7.29 (m, 5H, ArH), 4.61 (s, 2H, CH2),
1.87 (br s, 1H, OH)。
Embodiment two: pinacol borine and benzoic acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask benzoic acid (60.3 mg, 0.5
Mmol), pinacol borine (289 μ L, 2 mmol) is added with liquid-transfering gun, reacts 6 hours at room temperature, reaction is removed into gloves
Case, reaction was completed obtains borate, with equal trimethoxy-benzene (83.05 mg, 0.5 mmol) for internal standard, is dissolved, is stirred with CDCl3
It mixes 10 minutes, samples, match nuclear-magnetism.Being computed 1H yield is 90%.The nuclear magnetic data of product: 1H NMR (400 MHz,
CDCl3): δ 7.22-7.32 (m, 5H, ArH), 4.92 (s, 2H, CH2), 1.26 (s, 36H, CH3).To taking
1g silica gel is added in sample residue and reacts 3h at 50 DEG C using 3mL methanol as solvent, borate is further hydrolyzed to alcohol, is reacted
After, it is extracted with ethyl acetate three times, merges organic layer, it is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, passes through silica gel
(100-200 mesh) is column chromatography eluting, uses ethyl acetate/hexane (1:5) mixture as eluant, eluent, obtains pure primary alconol, point
It is 85% from yield.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.22-7.29 (m, 5H,
ArH), 4.61 (s, 2H, CH2), 1.87 (br s, 1H, OH)。
Embodiment three: pinacol borine and benzoic acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask benzoic acid (59.9 mg, 0.5
Mmol), pinacol borine (289 μ L, 2 mmol) is added with liquid-transfering gun, reacts 12 hours at room temperature, reaction is removed into hand
Casing is dissolved with equal trimethoxy-benzene (82.50 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, and core is matched in sampling
Magnetic.Being computed 1H yield is 99%；The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.22-7.32
(m, 5H, ArH), 4.92 (s, 2H, CH2), 1.26 (s, 36H, CH3).1g silica gel is added into sampling residue,
Using 3mL methanol as solvent, 3h is reacted at 50 DEG C, borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate
Three times, merge organic layer, it is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, it is pure by silica gel (100-200 mesh) column chromatography
Change, uses ethyl acetate/hexane (1:5) mixture as eluant, eluent, obtain pure primary alconol, separation yield is 92%.The nuclear-magnetism of product
Data: 1H NMR (400 MHz, CDCl3): δ 7.22-7.29 (m, 5H, ArH), 4.61 (s, 2H, CH2),
1.87 (br s, 1H, OH)。
Example IV: pinacol borine and benzoic acid 5:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask benzoic acid (60.8 mg, 0.5
Mmol), pinacol borine (362 μ L, 2.5 mmol) is added with liquid-transfering gun, reacts 9 hours at room temperature, reaction is removed into hand
Casing is dissolved with equal trimethoxy-benzene (83.74 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, and core is matched in sampling
Magnetic.Being computed 1H yield is 99%；Anhydrous Isosorbide-5-Nitrae-the dioxane of 0.5mL, product yield 18% is added in reaction system.The nuclear-magnetism of product
Data: 1H NMR (400 MHz, CDCl3): δ 7.22-7.32 (m, 5H, ArH), 4.92 (s, 2H, CH2),
1.26 (s, 36H, CH3).1g silica gel is added into sampling residue and reacts 3h at 50 DEG C using 3mL methanol as solvent, by boron
Acid esters is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merges organic layer, dry with anhydrous sodium sulfate,
Solvent is removed under reduced pressure, it is column chromatography eluting by silica gel (100-200 mesh), use ethyl acetate/hexane (1:5) mixture as washing
De- agent, obtains pure primary alconol, and separation yield is 92%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ
7.22– 7.29 (m, 5H, ArH), 4.61 (s, 2H, CH2), 1.87 (br s, 1H, OH)。
Embodiment five: pinacol borine and 4- fluobenzoic acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask 4- fluobenzoic acid (70.8 mg,
0.5 mmol), pinacol borine (290 μ L, 2 mmol) is added with liquid-transfering gun, reacts 12 hours at room temperature, reaction is moved
Glove box out is dissolved with equal trimethoxy-benzene (84.99 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, sampling,
With nuclear-magnetism.Being computed 1H yield is 90%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): 7.22 (br of δ
S, 2H, ArCH), 6.92 (t, 2H, ArCH), 4.76 (s, 2H, OCH2), 1.16 (s, 36H, CH3).To sampling
1g silica gel is added in residue and reacts 3h at 50 DEG C using 3mL methanol as solvent, borate is further hydrolyzed to alcohol, reaction knot
Shu Hou is extracted with ethyl acetate three times, merges organic layer, dry with anhydrous sodium sulfate, and solvent is removed under reduced pressure, passes through silica gel
(100-200 mesh) is column chromatography eluting, uses ethyl acetate/hexane (1:5) mixture as eluant, eluent, obtains pure primary alconol, point
It is 90% from yield.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.24 (br s, 2H, ArCH),
6.98 (t, 2H, ArCH), 4.56 (s, 2H, CH2), 2.27 (br s, 1H, OH).
Embodiment six: pinacol borine and 4- bromobenzoic acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask 4- bromobenzoic acid (100 mg,
0.5 mmol), pinacol borine (289 μ L, 2 mmol) is added with liquid-transfering gun, reacts 12 hours at room temperature, reaction is removed
Glove box is dissolved with equal trimethoxy-benzene (83.67 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, sampling,
With nuclear-magnetism.Being computed 1H yield is 95%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): 7.41 (br of δ
s, 2H, ArCH), 7.18 (t, 2H, ArCH), 4.82 (s, 2H, OCH2), 1.21 (s, 36H, CH3).To taking
1g silica gel is added in sample residue and reacts 3h at 50 DEG C using 3mL methanol as solvent, borate is further hydrolyzed to alcohol, is reacted
After, it is extracted with ethyl acetate three times, merges organic layer, it is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, passes through silica gel
(100-200 mesh) is column chromatography eluting, uses ethyl acetate/hexane (1:5) mixture as eluant, eluent, obtains pure primary alconol, point
It is 93% from yield.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.41 (br s, 2H, ArCH),
7.19 (t, 2H, ArCH), 4.60 (s, 2H, CH2), 2.26 (br s, 1H, OH)。
Embodiment seven: pinacol borine and O-Anisic Acid 4:1 molar ratio
Under inert gas N2 atmosphere, O-Anisic Acid (76.2 is added in by dehydration and deoxidation treated reaction flask
Mg, 0.5 mmol), pinacol borine (290 μ L, 2 mmol) is added with liquid-transfering gun, reacts 12 hours, will react at room temperature
Glove box is removed, with equal trimethoxy-benzene (84.23 mg, 0.5 mmol) for internal standard, is dissolved with CDCl3, stirs 10 minutes, takes
Sample matches nuclear-magnetism.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.42
(d, 1H, ArCH), 7.23 (t, 1H, ArCH), 6.96 (t, 1H, ArCH), 6.84 (d, 1H, ArCH),
4.98 (s,2H,OCH2), 1.27 (s,36H,CH3).1g silica gel is added into sampling residue, using 3mL methanol as solvent,
3h is reacted at 50 DEG C, borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merges organic layer,
It is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, it is column chromatography eluting by silica gel (100-200 mesh), use ethyl acetate/hexane
(1:5) mixture obtains pure primary alconol as eluant, eluent, and separation yield is 90%.The nuclear magnetic data of product: 1H NMR (400
MHz, CDCl3): δ 7.42 (d, 1H, ArCH), 7.23 (t, 1H, ArCH), 6.96 (t, 1H, ArCH),
6.84 (d, 1H, ArCH), 4.69 (s, 2H, CH2), 3.87 (br s, 1H, OH), 1.23 (s,3H,CH3)。
Embodiment eight: pinacol borine and 1- naphthoic acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask 1- naphthoic acid (85.4 mg,
0.5 mmol is added pinacol borine (289 μ L, 2 mmol) with liquid-transfering gun, reacts 12 hours at room temperature, reaction is removed
Glove box is dissolved with equal trimethoxy-benzene (83.42 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, sampling,
With nuclear-magnetism.Being computed 1H yield is 91%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 8.02 (d,
1H, ArCH), 7.80-7.82 (m, 2H, ArCH), 7.75(d, 1H, ArCH), 7.38-7.48 (m, 3H,
ArCH), 5.37 (s, 2H, OCH2 ), 1.23 (s, 36H, CH3).1g silica gel is added into sampling residue, with 3mL
Methanol is solvent, reacts 3h at 50 DEG C, and borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times,
Merge organic layer, it is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, it is column chromatography eluting by silica gel (100-200 mesh), use second
Acetoacetic ester/hexane (1:5) mixture obtains pure primary alconol as eluant, eluent, and separation yield is 91%.The nuclear magnetic data of product: 1H
NMR (400 MHz, CDCl3): δ 8.02 (d, 1H, ArCH), 7.80-7.82 (m, 2H, ArCH), 7.73 (d,
1H, ArCH), 7.38-7.48 (m, 3H, ArCH), 5.01 (s, 2H, CH2), 2.31 (br s, 1H, OH)。
Embodiment nine: pinacol borine and 4- p t butylbenzoic acid 4:1 molar ratio
Under inert gas N2 atmosphere, 4- p t butylbenzoic acid (88.9 is added in by dehydration and deoxidation treated reaction flask
Mg, 0.5 mmol are added pinacol borine (290 μ L, 2 mmol) with liquid-transfering gun, react 12 hours, will react at room temperature
Glove box is removed, with equal trimethoxy-benzene (83.89 mg, 0.5 mmol) for internal standard, is dissolved with CDCl3, stirs 10 minutes, takes
Sample matches nuclear-magnetism.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.28 (
d, 2H, ArCH), 7.19 (d, 2H, ArCH) , 4.82 (s, 2H, OCH2 ), 1.23 (s, 9H, CH3,
tBu), 1.18 (s, 36H, CH3).1g silica gel is added into sampling residue to react at 50 DEG C using 3mL methanol as solvent
Borate is further hydrolyzed to alcohol by 3h, after reaction, is extracted with ethyl acetate three times, is merged organic layer, use anhydrous slufuric acid
Sodium is dry, and solvent is removed under reduced pressure, column chromatography eluting by silica gel (100-200 mesh), is mixed with ethyl acetate/hexane (1:5)
Object obtains pure primary alconol as eluant, eluent, and separation yield is 92%.The nuclear magnetic data of product: 1H NMR (400 MHz,
CDCl3): δ 7.28 (d, 2H, ArCH), 7.19 (d, 2H, ArCH), 4.51 (s, 2H, CH2), 2.12
(br s, 1H, OH), 1.23 (s, 9H, CH3, tBu)。
Embodiment ten: pinacol borine and 2- bromobenzoic acid 4:1 molar ratio
Under inert gas N2 atmosphere, 2- bromobenzoic acid (100.6 is added in by dehydration and deoxidation treated reaction flask
Mg, 0.5 mmol are added pinacol borine (290 μ L, 2 mmol) with liquid-transfering gun, react 12 hours, will react at room temperature
Glove box is removed, with equal trimethoxy-benzene (84.17 mg, 0.5 mmol) for internal standard, is dissolved with CDCl3, stirs 10 minutes, takes
Sample matches nuclear-magnetism.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.41
(d, 2H, ArCH), 7.19-7.22 (m, 1H, ArCH), 7.03 (t, 1H, ArCH), 4.90 (s, 2H,
OCH2), 1.19 (s, 36H, CH3).1g silica gel is added into sampling residue to react at 50 DEG C using 3mL methanol as solvent
Borate is further hydrolyzed to alcohol by 3h, after reaction, is extracted with ethyl acetate three times, is merged organic layer, use anhydrous slufuric acid
Sodium is dry, and solvent is removed under reduced pressure, column chromatography eluting by silica gel (100-200 mesh), is mixed with ethyl acetate/hexane (1:5)
Object obtains pure primary alconol as eluant, eluent, and separation yield is 91%.The nuclear magnetic data of product: 1H NMR (400 MHz,
CDCl3): δ 7.41 (d, 2H, ArCH), 7.19-7.22 (m, 1H, ArCH), 7.03 (t, 1H, ArCH),
4.71 (s, 2H, CH2), 2.41 (br s, 1H, OH)。
Embodiment 11: pinacol borine and 4- iodo-benzoic acid 4:1 molar ratio
Under inert gas N2 atmosphere, 4- iodo-benzoic acid (124.0 is added in by dehydration and deoxidation treated reaction flask
Mg, 0.5 mmol are added pinacol borine (290 μ L, 2 mmol) with liquid-transfering gun, react 12 hours, will react at room temperature
Glove box is removed, with equal trimethoxy-benzene (84.09 mg, 0.5 mmol) for internal standard, is dissolved with CDCl3, stirs 10 minutes, takes
Sample matches nuclear-magnetism.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.57
(d, 2H, ArCH), 7.02 (d, 2H, ArCH), 4.78 (s, 2H, OCH2), 1.18 (s, 36H, CH3).To
1g silica gel is added in sampling residue and reacts 3h at 50 DEG C using 3mL methanol as solvent, borate is further hydrolyzed to alcohol, instead
After answering, it is extracted with ethyl acetate three times, merges organic layer, it is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, passes through silica gel
(100-200 mesh) is column chromatography eluting, uses ethyl acetate/hexane (1:5) mixture as eluant, eluent, obtains pure primary alconol, point
It is 94% from yield.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.57 (d, 2H, ArCH), 7.02
(d, 2H, ArCH), 4.65 (s, 2H, CH2), 2.15 (br s, 1H, OH)。
Embodiment 12: pinacol borine and 3- benzenpropanoic acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask 3- benzenpropanoic acid (74.9 mg,
0.2 mmol is added pinacol borine (289 μ L, 2 mmol) with liquid-transfering gun, reacts 10 hours at room temperature, reaction is removed
Glove box is dissolved with equal trimethoxy-benzene (83.89 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, and sampling is matched
Nuclear-magnetism.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.18 (t, 2H,
,ArCH), 7.05- 7.10 (m, 3H, ArCH), 3.80 (t, 2H, CH2, OCH2), 2.62 (t, 2H, CH2),
1.76-1.83 (m, 2H, CH2), 1.17 (s, 36H, CH3).1g silica gel is added into sampling residue, with 3mL methanol
For solvent, 3h is reacted at 50 DEG C, borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merge
Organic layer, it is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, it is column chromatography eluting by silica gel (100-200 mesh), with acetic acid second
Ester/hexane (1:5) mixture obtains pure primary alconol as eluant, eluent, and separation yield is 93%.The nuclear magnetic data of product: 1H NMR
(400 MHz, CDCl3): δ 7.23 (t, 2H, ArCH), 7.11- 7.13 (m, 3H, ArCH), 3.60 (t,
2H, CH2, OCH2), 2.65 (t, 2H, CH2), 1.78-1.85 (m, 2H, CH2), 1.61 (br s, 1H,
OH)。
Embodiment 13: pinacol borine and diphenyl acetic acid 4:1 molar ratio
Under inert gas N2 atmosphere, diphenyl acetic acid (105.8 is added in by dehydration and deoxidation treated reaction flask
Mg, 0.5 mmol are added pinacol borine (289 μ L, 2 mmol) with liquid-transfering gun, react 12 hours, will react at room temperature
Glove box is removed, with equal trimethoxy-benzene (83.84 mg, 0.5 mmol) for internal standard, is dissolved with CDCl3, stirs 10 minutes, takes
Sample matches nuclear-magnetism.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.14-
7.33 (m, 10H, ArCH), 4.42 (d, 2H, CH2, OCH2), 4.25 (t, 1H, CH), 1.24 (s,24H,
CH3, pinBOBpin), 1.13 (s, 12H, CH3, OBpin).1g silica gel is added into sampling residue, with 3mL methanol
For solvent, 3h is reacted at 50 DEG C, borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merge
Organic layer, it is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, it is column chromatography eluting by silica gel (100-200 mesh), with acetic acid second
Ester/hexane (1:5) mixture obtains pure primary alconol as eluant, eluent, and separation yield is 92%.The nuclear magnetic data of product: 1H NMR
(400 MHz, CDCl3): δ 7.20-7.31 (m, 10H, ArCH), 4.19 (t, 1H, CH), 4.13 (d, 2H,
CH2), 1.64-1.70 (t, 1H, OH)。
Embodiment 14: pinacol borine and the bromo- benzoic acid 4:1 molar ratio of 2- methyl -5-
Under inert gas N2 atmosphere, the bromo- benzoic acid of 2- methyl -5- is added in by dehydration and deoxidation treated reaction flask
(107.1 mg, 0.5 mmol are added pinacol borine (289 μ L, 2 mmol) with liquid-transfering gun, react 12 hours at room temperature,
Reaction is removed into glove box, with equal trimethoxy-benzene (83.77 mg, 0.5 mmol) for internal standard, is dissolved with CDCl3, stirring 10
Minute, nuclear-magnetism is matched in sampling.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ
6.91 (d, 1H, ArCH), 7.20 (d, 1H, ArCH), 7.48 (s, 1H, ArCH), 4.78 (s, 2H,
OCH2), 2.13 (s, 3H, CH3), 1.18 (s, 36H, CH3).1g silica gel is added into sampling residue, with 3mL first
Alcohol is solvent, reacts 3h at 50 DEG C, and borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, closes
And organic layer, it is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, it is column chromatography eluting by silica gel (100-200 mesh), use acetic acid
Ethyl ester/hexane (1:5) mixture obtains pure primary alconol as eluant, eluent, and separation yield is 92%.The nuclear magnetic data of product: 1H
NMR (400 MHz, CDCl3): δ 6.91 (d, 1H, ArCH), 7.22 (d, 1H, ArCH), 7.57 (s, 1H,
ArCH), 4.44 (s, 2H, OCH2), 2.13 (s, 3H, CH3),2.25 (br s, 1H, OH)。
Embodiment 15: pinacol borine and 2- phenylbutyric acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask 2- phenylbutyric acid (82.2 mg,
0.5 mmol is added pinacol borine (290 μ L, 2 mmol) with liquid-transfering gun, reacts 12 hours at room temperature, reaction is removed
Glove box is dissolved with equal trimethoxy-benzene (84.20 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, sampling,
With nuclear-magnetism.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.16-7.20
(m, 2H, ArCH), 7.09-7.11 (m, 3H, ArCH),
3.84-3.94 (m, 2H, CH2, OCH2), 2.58-2.67 (m, 1H, CH), 1.71-1.80 (m, 1H,
CH2), 1.47-1.56 (m, 1H, CH2), 1.17 (s, 36H, CH3, OBpin & pinBOBpin), 0.75 (t,
3H, CH3).1g silica gel is added into sampling residue and reacts 3h at 50 DEG C using 3mL methanol as solvent, borate is further
It is hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merges organic layer, it is dry with anhydrous sodium sulfate, it is removed under reduced pressure molten
Agent, it is column chromatography eluting by silica gel (100-200 mesh), it uses ethyl acetate/hexane (1:5) mixture as eluant, eluent, obtains
Pure primary alconol, separation yield are 92%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.17-7.30
(m, 5H, ArCH), 3.66-3.68 (m, 2H, CH2,OCH2), 2.64 (m, 1H, CH), 1.54-1.73 (m,
1H, CH2), 1.87(s,1H, OH), 0.81 (t, 3H, CH3)。
Embodiment 16: pinacol borine and indole-3-acetic acid 5:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask 3-indolyl acetic acid (88.0 mg,
0.5 mmol is added pinacol borine (363 μ L, 2.5 mmol) with liquid-transfering gun, reacts 12 hours at room temperature, reaction is moved
Glove box out is dissolved with equal trimethoxy-benzene (84.49 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, is taken
Sample matches nuclear-magnetism.Being computed 1H yield is 95%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.83
(d, 1H, ArCH), 7.46 (d, 1H, ArCH), 7.03-7.15 (m, 3H, ArCH), 4.07 (t, 2H,
OCH2), 2.91 (t, 2H, CH2), 1.30 (s, 12H, CH3, N-Bpin), 1.15 (s, 24H, CH3,
pinBOBpin), 1.07 (s, 12H, CH3, OBpin).1g silica gel is added into sampling residue, is molten with 3mL methanol
Agent reacts 3h at 50 DEG C, borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merges organic
Layer, it is dry with anhydrous sodium sulfate, solvent is removed under reduced pressure, it is column chromatography eluting by silica gel (100-200 mesh), with ethyl acetate/
Hexane (1:5) mixture obtains pure primary alconol as eluant, eluent, and separation yield is 92%.The nuclear magnetic data of product: 1H NMR
(400 MHz, CDCl3): δ 8.10 (s, 1H, NH), 7.83 (d, 1H, ArCH), 7.46 (d, 1H, ArCH),
7.03-7.15 (m, 3H, ArCH), 4.67 (t, 2H, OCH2), 3.28 (t, 2H, CH2), 1.90 (br s,
1H, OH)。
Embodiment 17: pinacol borine and o-carboxyl phenylacetic acid 7:1 molar ratio
Under inert gas N2 atmosphere, o-carboxyl phenylacetic acid (90.0 is added in by dehydration and deoxidation treated reaction flask
Mg, 0.5 mmol are added pinacol borine (508 μ L, 3.5 mmol) with liquid-transfering gun, react 11 hours at room temperature, will be anti-
Glove box should be removed, with equal trimethoxy-benzene (84.02 mg, 0.5 mmol) for internal standard, is dissolved with CDCl3, is stirred 10 minutes,
Nuclear-magnetism is matched in sampling.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.34
(br s, 1H, ArCH), 7.12 (br s, 3H, ArCH), 4.91 (s, 2H, CH2), 3.97 (t, 2H,
CH2), 2.87 (t, 2H, CH2), 1.18 (s, 72H, CH3, OBpin & pinBOBpin).Into sampling residue
1g silica gel is added and reacts 3h at 50 DEG C using 3mL methanol as solvent, borate is further hydrolyzed to alcohol, after reaction, uses
Ethyl acetate extracts three times, merges organic layer, dry with anhydrous sodium sulfate, and solvent is removed under reduced pressure, passes through silica gel (100-200 mesh)
It is column chromatography eluting, it uses ethyl acetate/hexane (1:5) mixture as eluant, eluent, obtains pure primary alconol, separation yield is 92%.
The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 7.34 (br s, 1H, ArCH), 7.12 (br s,
3H, ArCH), 4.54 (s, 2 H, CH2), 3.76 (t, 2 H, CH2OH), 3.7 (br, 1 H, OH), 3.1
(br s, 1 H, OH), 2.86 (t, 2 H, CH2)。
The reaction of the embodiment of the present invention carries out in glove box；The present invention is the aromatic carboxylic acid under solvent-free catalysis-free agent
Hydroboration, meet the principle of Green Chemistry.
Claims (10)
1. a kind of method for preparing alcoholic compound by the non-catalytic reaction of aromatic carboxylic acid, which is characterized in that include the following steps,
It is solvent-free, without under catalyst, aromatic carboxylic acid and borine carry out hydroboration；Silica gel, first are added after hydroboration
Alcohol, hydrolysis prepare alcoholic compound.
2. the method for preparing alcoholic compound by the non-catalytic reaction of aromatic carboxylic acid according to claim 1, which is characterized in that
The borine is pinacol borine；The aromatic carboxylic acid is benzoic acid, 4- bromobenzoic acid, 4- fluobenzoic acid, 1- naphthoic acid, 2-
Methoxy benzoic acid, 4- p t butylbenzoic acid, 4- ethoxybenzoic acid, 2- bromobenzoic acid, 4- iodo-benzoic acid, 3- benzenpropanoic acid, two
Phenylacetic acid, 2- phenylbutyric acid, indole-3-acetic acid, o-carboxyl phenylacetic acid or 2- methyl -5- bromobenzoic acid.
3. the method for preparing alcoholic compound by the non-catalytic reaction of aromatic carboxylic acid according to claim 1, which is characterized in that
The molar ratio of the aromatic carboxylic acid and borine is 1:3~1:7；The temperature of the hydroboration is room temperature；The hydroboration
The time of reaction is 6~12 hours.
4. the method for preparing alcoholic compound by the non-catalytic reaction of aromatic carboxylic acid according to claim 1, which is characterized in that
The hydroboration carries out under atmosphere of inert gases；The condition of hydrolysis is to react 3h at 50 DEG C.
5. the method for preparing alcoholic compound by the non-catalytic reaction of aromatic carboxylic acid according to claim 1, which is characterized in that
The amount ratio of aromatic carboxylic acid and silica gel, methanol is 1mmoL:2g:6mL.
6. aromatic carboxylic acid and borine are preparing the application in alcoholic compound as raw material, which is characterized in that prepare alcoholic compound
Include the following steps, solvent-free, without under catalyst, aromatic carboxylic acid and borine carry out hydroboration；Hydroboration terminates
Silica gel, methanol are added afterwards, hydrolysis prepares alcoholic compound.
7. application according to claim 6, which is characterized in that the borine is pinacol borine；The aromatic carboxylic acid
For benzoic acid, 4- bromobenzoic acid, 4- fluobenzoic acid, 1- naphthoic acid, O-Anisic Acid, 4- p t butylbenzoic acid, 4- ethoxy
Yl benzoic acid, 2- bromobenzoic acid, 4- iodo-benzoic acid, 3- benzenpropanoic acid, diphenyl acetic acid, 2- phenylbutyric acid, indole-3-acetic acid, neighbour
Carboxylphenylaceticacid acid or 2- methyl -5- bromobenzoic acid.
8. application according to claim 6, which is characterized in that the molar ratio of the aromatic carboxylic acid and borine be 1:3~
1:7；The temperature of the hydroboration is room temperature；The time of the hydroboration is 6~12 hours；The hydroboration
It is carried out under atmosphere of inert gases.
9. application according to claim 6, which is characterized in that the condition of hydrolysis is to react 3h at 50 DEG C.
10. application according to claim 6, which is characterized in that the amount ratio of aromatic carboxylic acid and silica gel, methanol is
1mmoL:2g:6mL。
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| CN111760593A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Application of deprotonated phenyl bridged beta-ketimine lithium compound in hydroboration reaction |
| CN111763135A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Application of deprotonated phenyl bridged beta-ketimine lithium compound in preparation of alcohol from ester |
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| CN111760593A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Application of deprotonated phenyl bridged beta-ketimine lithium compound in hydroboration reaction |
| CN111763135A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Application of deprotonated phenyl bridged beta-ketimine lithium compound in preparation of alcohol from ester |
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