CN109503318A - A method of alcoholic compound is prepared by the non-catalytic reaction of aliphatic carboxylic acid - Google Patents
A method of alcoholic compound is prepared by the non-catalytic reaction of aliphatic carboxylic acid Download PDFInfo
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- CN109503318A CN109503318A CN201811585436.6A CN201811585436A CN109503318A CN 109503318 A CN109503318 A CN 109503318A CN 201811585436 A CN201811585436 A CN 201811585436A CN 109503318 A CN109503318 A CN 109503318A
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- Prior art keywords
- carboxylic acid
- aliphatic carboxylic
- acid
- borine
- hydroboration
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- 150000007933 aliphatic carboxylic acids Chemical class 0.000 title claims abstract description 31
- 230000001476 alcoholic effect Effects 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 13
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910000085 borane Inorganic materials 0.000 claims abstract description 39
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006197 hydroboration reaction Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims abstract description 12
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 229940005605 valeric acid Drugs 0.000 claims abstract description 6
- 239000001361 adipic acid Substances 0.000 claims abstract description 5
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000741 silica gel Substances 0.000 claims description 23
- 229910002027 silica gel Inorganic materials 0.000 claims description 23
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract description 15
- 230000018044 dehydration Effects 0.000 abstract description 9
- 238000006297 dehydration reaction Methods 0.000 abstract description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 48
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 239000002904 solvent Substances 0.000 description 18
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 238000005070 sampling Methods 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 230000005311 nuclear magnetism Effects 0.000 description 8
- 229940030010 trimethoxybenzene Drugs 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- -1 boric acid ester Chemical class 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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
- 229960002645 boric acid Drugs 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-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
- 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 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-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
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change 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
- 239000000284 extract Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 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
- 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)
- 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 aliphatic 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 8-10 hours；The carboxylic acid is acetic acid, caproic acid, valeric acid, enanthic acid, trimethylace tonitric, adipic acid etc..Efficiently with borine hydroboration occurs for the present invention using aliphatic 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 and provides new scheme.
Description
Technical field
The present invention relates to the application fields of Green Chemistry, and in particular to a kind of non-catalytic reaction preparation by aliphatic carboxylic acid
The method of alcoholic compound.
Background technique
Organic boric acid ester is considered as orthoboric acid B (OH)3In hydrogen replaced by organic group after derivative, alkylboronic acids
Ester can conveniently be converted into alcohol, and alcohol is many synthesis conversions, the important component of drug and materials synthesis.In recent years, chemical work
Authors develop various catalyst, the hydroboration applied to carbonyls and borine.
Carboxylic acid and the difference of aldehyde ketone nucleophilic addition activity: (1) active hydrogen of carboxylic acid is easily left away, therefore its two O realities
It is of equal value on border, so the steric hindrance of carboxyl is larger from the point of view of space structure, and the presence of carboxyl hydrogen bond, makes entire carbonyl
Cloud density it is larger, nucleopilic reagent attack activated centre is more difficult；(2) nucleopilic reagent elder generation attack carbonyl carbon, this and carbon
On cloud density it is related, the small first attack of density, such as aldehyde ketone are smaller than the cloud density of ester, amide, so active
Height, can preferential reaction, three-dimensional effect it is big be not easy to react；(3) to see that leaving group, aldehyde ketone are left away when forming transition state
Group is alkyl and hydrogen, and the two is all not easy to leave away, so addition only occurs for aldehyde ketone, does not eliminate, and different from carboxylic acid and its is spread out
Biology.The reduction catalysts system about synthesis borate reported on document at present mainly utilizes LiAlH4And NaBH4, SmI2-
H2O-Et3N and the carboxylic acid hydroboration of various transition metal compound catalizers catalysis.But these methods have apparent lack
Point: LiAlH4And NaBH4System security risk is very big, SmI2-H2O-Et3N system needs excessive many reagents, and transition metal is matched
Objects system is closed to need to carry out under high temperature and high pressure.
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.
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 aliphatic carboxylic acid, is included the following steps, it is solvent-free, without catalysis
Under agent, aliphatic carboxylic acid and borine carry out hydroboration；Silica gel, methanol, hydrolysis system are added after hydroboration
Standby alcoholic compound.
Aliphatic 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, aliphatic 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 aliphatic carboxylic acid is acetic acid, caproic acid, valeric acid, enanthic acid, three
Methyl acetic acid or adipic acid.
In the present invention, the hydroboration carries out under atmosphere of inert gases.It is contacted after the hydroboration
Air stopped reaction obtains borate, is further hydrolyzed to alcoholic compound.
In the present invention, the molar ratio of the aliphatic carboxylic acid and borine is 1:3~1:7；Aliphatic carboxylic acid and silica gel, first
The amount ratio of alcohol is 1mmoL:2g:5mL.
In the present invention, the temperature of the hydroboration is room temperature；The time of the hydroboration is 8~10 hours.
In the present invention, the condition of hydrolysis is to react 3h at 50 DEG C.After reaction, it 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 acetic acid second
Ester/hexane (1:5 volume ratio) mixture as eluant, eluent, obtains alcoholic compound.
Aliphatic carboxylic acid is generally liquid, and aliphatic carboxylic acid is reacted with pinacol borine for homogeneous reaction.
Above-mentioned technical proposal can be expressed as follows:
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 aliphatic carboxylic acid and pinacol borine hydroboration it is anti-
It answers, and hydrolysis obtains alcohol in limited conditions, to develop a kind of method for preparing alcoholic compound of efficient green.
2. the present invention can at room temperature high activity progress aliphatic carboxylic acid and borine hydroboration, reaction
It carries out 8-10 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
Aliphatic carboxylic acid, be combined to provide more more options for the industry of borate；And reaction process is simply 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 acetic acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask acetic acid (28.6 μ L,
0.5mmol), pinacol borine (290 μ L, 2 mmol) is added with liquid-transfering gun, reacts 10 hours at room temperature, reaction is removed
Glove box, stopped reaction obtain borate, and sampling matches nuclear-magnetism, is interior with equal trimethoxy-benzene (84.08 mg, 0.5 mmol)
Mark, is dissolved with CDCl3, is stirred 10 minutes, and being computed 1H yield is 99%；Acetic acid is replaced with into equimolar acetaldehyde, is unable to get production
Object.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 3.89 (q, 2H, CH2), 1.26 (s, 36H,
CH3), 1.22 (br s, 3H, CH3).1g silica gel is added into sampling residue, using 2.5mL methanol as solvent, at 50 DEG C
3h is reacted, borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merges organic layer, use is anhydrous
Sodium sulphate is dry, and solvent is removed under reduced pressure, 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 3.69 (q, 2H, CH2), 2.92 (br s, 1H, OH), 1.22 (br s, 3H, CH3).
Embodiment two: pinacol borine and valeric acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask valeric acid (54.38 μ L,
0.5mmol), pinacol borine (290 μ L, 2 mmol) is added with liquid-transfering gun, reacts 10 hours at room temperature, reaction is removed
Glove box is dissolved with equal trimethoxy-benzene (84.12 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, sampling,
With nuclear-magnetism.Being computed 1H yield is 92%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 3.82 (t,
2H, OCH2), 1.53-1.57 (m, 2H, CH2), 1.31-1.53 (m, 4H, CH2), 1.29(s, 36H, CH),
0.87 (t, 3H, CH3).1g silica gel is added into sampling residue and reacts 3h at 50 DEG C using 2.5mL methanol as solvent, it will
Borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merges organic layer, dry with anhydrous sodium sulfate
It is dry, solvent is removed under reduced pressure, it is column chromatography eluting by silica gel (100-200 mesh), made with ethyl acetate/hexane (1:5) mixture
For eluant, eluent, pure primary alconol is obtained, separation yield is 85%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ
3.63 (t, 2H, OCH2), 1.57 (m, 2H, CH2), 1.35 (m, 2H, CH2), 2.35(br s, 1H, OH),
0.91 (t, 3H, CH3)。
Embodiment three: pinacol borine and caproic acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask caproic acid (62.52 μ L,
0.5mmol), pinacol borine (290 μ L, 2 mmol) is added with liquid-transfering gun, reacts 10 hours at room temperature, reaction is removed
Glove box is dissolved with equal trimethoxy-benzene (84.01 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): δ 3.77 (t,
2H, OCH2), 1.47-1.53 (m, 2H, CH2), 1.25-1.36 (m, 6H, CH2), 1.20(s, 48H, CH3),
0.83 (t, 3H, CH3).1g silica gel is added into sampling residue and reacts 3h at 50 DEG C using 2.5mL methanol as solvent, it will
Borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merges organic layer, dry with anhydrous sodium sulfate
It is dry, solvent is removed under reduced pressure, it is column chromatography eluting by silica gel (100-200 mesh), made with ethyl acetate/hexane (1:5) mixture
For eluant, eluent, pure primary alconol is obtained, separation yield is 82%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ
3.75 (t, 2H, OCH2), 1.47-1.53 (m, 2H, CH2), 1.25-1.36 (m, 6H, CH2), 1.72(br s,
1H, OH), 0.83 (t, 3H, CH3).
Example IV: pinacol borine and enanthic acid 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask enanthic acid (70.90 μ L,
0.5mmol), pinacol borine (290 μ L, 2 mmol) is added with liquid-transfering gun, reacts 10 hours at room temperature, reaction is removed
Glove box is dissolved with equal trimethoxy-benzene (84.05 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): δ 3.72 (t,
2H, OCH2), 1.42-1.48 (m, 2H, CH2), 1.20-1.31 (m, 8H, CH2), 1.15(s, 48H, CH3),
0.78 (t, 3H, CH3).1g silica gel is added into sampling residue and reacts 3h at 50 DEG C using 2.5mL methanol as solvent, it will
Borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merges organic layer, dry with anhydrous sodium sulfate
It is dry, solvent is removed under reduced pressure, it is column chromatography eluting by silica gel (100-200 mesh), made with ethyl acetate/hexane (1:5) mixture
For eluant, eluent, pure primary alconol is obtained, separation yield is 82%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ
3.72 (t, 2H, OCH2), 1.42-1.48 (m, 2H, CH2), 1.20-1.31 (m, 8H, CH2), 1.75(br s,
1H, OH), 0.78 (t, 3H, CH3).
Embodiment five: pinacol borine and acetic acid 3:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask acetic acid (28.6 μ L,
0.5mmol), pinacol borine (218 μ L, 1.5 mmol) is added with liquid-transfering gun, reacts 10 hours at room temperature, reaction is moved
Glove box out is dissolved with equal trimethoxy-benzene (84.08 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%；Anhydrous 0.5mL1,4- dioxane, product yield 16% is added in reaction system.It produces
The nuclear magnetic data of object: 1H NMR (400 MHz, CDCl3): δ 3.89 (q, 2H, CH2), 1.26 (s, 36H,
CH3), 1.22 (br s, 3H, CH3).1g silica gel is added into sampling residue, using 2.5mL methanol as solvent, at 50 DEG C
3h is reacted, borate is further hydrolyzed to alcohol, after reaction, is extracted with ethyl acetate three times, merges organic layer, use is anhydrous
Sodium sulphate is dry, and solvent is removed under reduced pressure, 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 90%.The nuclear magnetic data of product: 1H NMR (400 MHz,
CDCl3): δ 3.69 (q, 2H, CH2), 2.92 (br s, 1H, OH), 1.22 (br s, 3H, CH3).
Embodiment six: pinacol borine and acetic acid 5:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask acetic acid (28.6 μ L,
0.5mmol), pinacol borine (363 μ L, 2.5 mmol) is added with liquid-transfering gun, reacts 10 hours at room temperature, reaction is moved
Glove box out is dissolved with equal trimethoxy-benzene (84.08 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, is taken
Sample matches nuclear-magnetism.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 3.89
(q, 2H, CH2), 1.26 (s, 36H, CH3), 1.22 (br s, 3H, CH3).1g silicon is added into sampling residue
Glue reacts 3h at 50 DEG C using 2.5mL methanol as solvent, and borate is further hydrolyzed to alcohol, after reaction, with acetic acid second
Ester 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) column chromatography
Method purifying uses ethyl acetate/hexane (1:5) mixture as eluant, eluent, obtains pure primary alconol, and separation yield is 92%.Product
Nuclear magnetic data: 1H NMR (400 MHz, CDCl3): δ 3.69 (q, 2H, CH2), 2.92 (br s, 1H, OH),
1.22 (br s, 3H, CH3)。
Embodiment seven: pinacol borine and trimethylace tonitric 4:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask trimethylace tonitric (50.7 mg,
0.5mmol), pinacol borine (289 μ L, 2 mmol) is added with liquid-transfering gun, reacts 10 hours at room temperature, reaction is removed
Glove box is dissolved with equal trimethoxy-benzene (84.08 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 3.44 (s,
2H, OCH2), 1.18 (s, 36H, CH3, OBpin & pinBOBpin), 0.83 (s, 9H, CH3).It is surplus to sampling
1g silica gel is added in excess and reacts 3h at 50 DEG C using 2.5mL 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 3.20 (s, 2H, OCH2), 1.97
(br s, 1H, OH), 0.83 (s, 9H, CH3)。
Embodiment eight: pinacol borine and adipic acid 7:1 molar ratio
Under inert gas N2 atmosphere, be added in by dehydration and deoxidation treated reaction flask adipic acid (72.9 mg,
0.5mmol), pinacol borine (508 μ L, 3.5 mmol) is added with liquid-transfering gun, reacts 10 hours at room temperature, reaction is moved
Glove box out is dissolved with equal trimethoxy-benzene (83.90 mg, 0.5 mmol) for internal standard with CDCl3, is stirred 10 minutes, is taken
Sample matches nuclear-magnetism.Being computed 1H yield is 99%.The nuclear magnetic data of product: 1H NMR (400 MHz, CDCl3): δ 3.78
(t, 4H, OCH2), 1.49-1.51 (m, 4H, CH2), 1.29-1.31 (m, 4H, CH2), 1.18 (s, 72H,
CH3, OBpin & pinBOBpin).1g silica gel is added into sampling residue to react at 50 DEG C using 2.5mL 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 3.75 (t, 4H, OCH2), 1.48-1.51 (m, 4H, CH2), 1.29-1.31 (m, 4H, CH2),
2.26 (br s,2H, OH)。
The reaction of the embodiment of the present invention carries out in glove box；The present invention is the boron hydrogen of the carboxylic acid under solvent-free catalysis-free agent
Change reaction, meets the principle of Green Chemistry.
Claims (10)
1. a kind of method for preparing alcoholic compound by the non-catalytic reaction of aliphatic carboxylic acid, which is characterized in that include the following steps,
It is solvent-free, without under catalyst, aliphatic 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 aliphatic carboxylic acid according to claim 1, which is characterized in that
The borine is pinacol borine；The aliphatic carboxylic acid be acetic acid, caproic acid, valeric acid, enanthic acid, trimethylace tonitric or oneself two
Acid.
3. the method for preparing alcoholic compound by the non-catalytic reaction of aliphatic carboxylic acid according to claim 1, which is characterized in that
The amount ratio of aliphatic carboxylic acid and silica gel, methanol is 1mmoL:2g:5mL.
4. the method for preparing alcoholic compound by the non-catalytic reaction of aliphatic carboxylic acid according to claim 1, which is characterized in that
The molar ratio of the aliphatic carboxylic acid and borine is 1:3~1:7.
5. the method for preparing alcoholic compound by the non-catalytic reaction of aliphatic carboxylic acid according to claim 1, which is characterized in that
The temperature of the hydroboration is room temperature；The time of the hydroboration is 8~10 hours.
6. the method for preparing alcoholic compound by the non-catalytic reaction of aliphatic carboxylic acid according to claim 1, which is characterized in that
The condition of hydrolysis is to react 3h at 50 DEG C；The hydroboration carries out under atmosphere of inert gases.
7. aliphatic 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, aliphatic carboxylic acid and borine carry out hydroboration；Hydroboration terminates
Silica gel, methanol are added afterwards, hydrolysis prepares alcoholic compound.
8. application according to claim 7, which is characterized in that the borine is pinacol borine；The aliphatic carboxylic acid
For acetic acid, caproic acid, valeric acid, enanthic acid, trimethylace tonitric or adipic acid.
9. application according to claim 7, which is characterized in that the hydroboration carries out under atmosphere of inert gases；
The molar ratio of the aliphatic carboxylic acid and borine is 1:3~1:7；The temperature of the hydroboration is room temperature；The hydroboration
The time of reaction is 8~10 hours.
10. application according to claim 7, which is characterized in that the condition of hydrolysis is to react 3h at 50 DEG C；Aliphatic
The amount ratio of carboxylic acid and silica gel, methanol is 1mmoL:2g:5mL.
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