CN113880688B - Synthesis method of diol - Google Patents

Synthesis method of diol Download PDF

Info

Publication number
CN113880688B
CN113880688B CN202111297256.XA CN202111297256A CN113880688B CN 113880688 B CN113880688 B CN 113880688B CN 202111297256 A CN202111297256 A CN 202111297256A CN 113880688 B CN113880688 B CN 113880688B
Authority
CN
China
Prior art keywords
formula
catalyst
reaction
diol
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111297256.XA
Other languages
Chinese (zh)
Other versions
CN113880688A (en
Inventor
邵银林
施茵茵
***
黄哲帆
王越
孙佳雯
姜含笑
吴瑶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of New Materials and Industrial Technology of Wenzhou University
Original Assignee
Institute of New Materials and Industrial Technology of Wenzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of New Materials and Industrial Technology of Wenzhou University filed Critical Institute of New Materials and Industrial Technology of Wenzhou University
Priority to CN202111297256.XA priority Critical patent/CN113880688B/en
Publication of CN113880688A publication Critical patent/CN113880688A/en
Application granted granted Critical
Publication of CN113880688B publication Critical patent/CN113880688B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a glycol synthesis method; the invention synthesizes diol compounds with diversified structures by catalyzing the hydroboration of lactone by lithium bis (trimethylsilyl) amide; in particular to a glycol compound prepared by taking various lactone compounds and pinacol borane as raw materials under a lithium bis (trimethylsilyl) amide catalytic system; the method has the advantages of wide raw material sources or easy preparation, simple and convenient operation, controllable selectivity, high yield, mild conditions and wide universality.

Description

Synthesis method of diol
Technical Field
The invention belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing glycol.
Background
The hydroboration reaction of lactones is relatively difficult due to the existence of larger steric hindrance, electronic effect and other factors, so that few examples are reported at present. In 2014, sadow et al reported in detail that tris (4, 4-dimethyl-2-oxazolinyl) phenylmagnesium borate methyl compound catalyzes the hydroboration of lactones (Chem Sci,2014,5,959-964); in 2017, nembenna et al utilized guanidino ligands directly with Mg { N (SiMe 3 ) 2 } 2 Two different methods of reacting or reacting guanidyl ligand potassium salt with magnesium chloride succeeded in synthesizing the corresponding guanidyl-stable magnesium amide (Dalton Trans,2017,46,4152-4156) and effecting hydroboration of the magnesium amide to the lactone. In 2020, cao et al reported complex magnesium complex-catalyzed hydroboration of lactones (Dalton Trans.2020,49, 2776-2780). However, these reported lactone borohydridesThe metal catalyst used has very complex structure and certain limitation.
Disclosure of Invention
The invention aims to provide a glycol synthesis method, which uses a simple catalyst, namely lithium bis (trimethylsilyl) amide to realize the method for synthesizing glycol by a hydroboration reaction of lactone.
The aim of the invention is realized by the following technical scheme:
a method for synthesizing glycol takes lithium bis (trimethylsilyl) amide (abbreviated as LiHMDS) as a catalyst, takes each compound shown in a formula I and a compound shown in a formula II as raw materials, and prepares the compound shown in the formula III through a hydroboration reaction, wherein the chemical reaction equation is as follows:
in the above formula, formula I is various lactone compounds (lactones with or without benzene rings); formula II is pinacolborane; formula III is a diol.
Preferably, R 1 Is phenyl or alkyl.
Preferably, the molar ratio is as follows: a compound of formula I: a compound of formula II: catalyst = 1.0:2.0:0.08.
preferably, the reaction temperature is 80 ℃ and the reaction time is 20 hours.
The reaction mechanism of the invention is shown in figure 1:
firstly, lithium silamide reacts with pinacol borane to generate a lithium hydride intermediate A, the intermediate A reacts with lactone to generate an intermediate B, the intermediate B reacts with pinacol borane to generate an intermediate C, the intermediate C reacts with the lithium hydride intermediate A to generate an intermediate D, the intermediate D reacts with pinacol borane to generate a boron oxide compound E, and finally the boron oxide compound E is hydrolyzed to obtain the product glycol.
The beneficial effects of the invention are as follows:
(1) The method has the advantages of high atom economy, good reaction universality, mild reaction conditions and no need of a large amount of/complicated additives.
(2) Compared with a complex metal catalyst, the nonmetal catalyst adopted by the invention has obvious advantages of the catalyst in realizing the hydroboration reduction reaction of the lactone, realizes the construction of alcohol compounds by base catalysis of the hydroboration of the lactone, and provides an important reference for the construction of glycol compounds.
(3) Compared with the prior method, the lithium bis (trimethylsilyl) amide catalyst is simple, does not need complex synthesis, has low price and can be purchased commercially.
Drawings
Fig. 1: the reaction mechanism diagram of the invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
The preparation of 1, 2-benzenedimethanol has the following structural formula:
under nitrogen protection, raw materials phthalide (1 mmol) and pinacol borane (2.0 mmol), catalyst LiHMDS (0.08 mmol), solvent toluene (1.0 mL) were added, reacted at 80℃for 20h, followed by 2mol/L NaOH/MeOH solution (i.e. 2mol sodium hydroxide per liter of methanol) and stirred at room temperature overnight. The product isolation yield was 89%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 ):δ7.24(s,4H),4.52(s,4H),4.46(s,2H). 13 C NMR(125MHz,CDCl 3 ):δ139.2,129.5,128.4,63.5.
example 2
Preparation of 2- (2- (hydroxymethyl) phenyl) ethanol, the structural formula is as follows:
under the protection of nitrogen, 3-isochromone (1 mmol) and pinacol borane (2.0 mmol) as raw materials, liHMDS (0.08 mol) as catalyst, toluene (1.0 mL) as solvent, were added, reacted at 80℃for 20h, then 2mol/L NaOH/MeOH solution (i.e. 2mol sodium hydroxide per liter of methanol) was added, and stirred at room temperature overnight. The product isolation yield was 91%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 )δ7.24(d,J＝8.0Hz,2H),7.17(t,J＝6.2Hz,2H),4.51(s,2H),4.32(bs,1H),3.73(t,J＝6.0Hz,2H),2.83(t,J＝5.9Hz,2H),2.40(bs,1H). 13 C NMR(125MHz,CDCl 3 )δ139.3,138.3,130.2,129.8,128.6,126.8,63.3,63.0,35.2.
example 3
The preparation of 1, 5-nonanediol has the following structural formula:
under nitrogen protection, delta-nonanolactone (1 mmol) and pinacol borane (2.0 mmol), catalyst LiHMDS (0.08 mmol), solvent toluene (1.0 mL) were added, reacted at 80℃for 20h, followed by 2mol/L NaOH/MeOH solution (i.e. 2mol sodium hydroxide per liter methanol) and stirred overnight at room temperature. The product isolation yield was 88%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 )δ3.54-3.59(m,3H),3.28(bs,1H),2.93(bs,1H),1.27-1.56(m,12H),0.85-0.88(m,3H). 13 C NMR(125MHz,CDCl 3 )δ71.7,62.4,37.3,36.9,32.5,28.0,22.8,21.9,14.1.
example 4
The preparation of 3-methyl-1, 4-octanediol has the following structural formula:
under nitrogen protection, raw materials whiskey lactone (1 mmol) and pinacol borane (2.0 mmol), catalyst LiHMDS (0.08 mmol), solvent toluene (1.0 mL) were added, reacted at 80℃for 20h, followed by 2mol/L NaOH/MeOH solution (i.e. 2mol sodium hydroxide per liter of methanol) and stirred overnight at room temperature. The product isolation yield was 87%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 )δ3.72-3.82(m,1H),3.53-3.69(m,2H),2.54-2.88(s,2H),1.63-1.82(m,2H),1.22-1.58(m,7H),0.85-1.04(m,6H). 13 C NMR(125MHz,CDCl 3 )δ75.1,60.6,36.1,35.4,34.3,28.2,22.9,16.7,14.0.
example 5
1, 4-butanediol is prepared, and the structural formula is as follows:
under nitrogen protection, delta-valerolactone (1 mmol) and pinacol borane (2.0 mmol), catalyst LiHMDS (0.08 mmol), solvent toluene (1.0 mL) were added and reacted at 80℃for 20h, followed by 2mol/L NaOH/MeOH solution (i.e. 2mol sodium hydroxide per liter methanol) and stirring at room temperature overnight. The product isolation yield was 86%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(400MHz,CDCl 3 )δ3.77-3.64(m,4H),1.97(s,2H),1.75-1.64(m,4H). 13 CNMR(125MHz,CDCl 3 )δ62.8,29.8.
example 6
The preparation of the 1, 4-pentanediol has the following structural formula:
under the protection of nitrogen, raw materials of gamma-valerolactone (1 mmol) and pinacol borane (2.0 mmol) and a catalyst LiHMDS are added
(0.08 mmol), toluene (1.0 mL), was reacted at 80℃for 20h, followed by addition of 2mol/L NaOH/MeOH solution (i.e., 2mol sodium hydroxide per liter of methanol) and stirring overnight at room temperature. The product isolation yield was 91%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(400MHz,CDCl 3 ):δ4.11(s,2H),3.88-3.73(m,1H),3.71-3.52(m,2H),1.77-1.41(m,4H),1.19(d,J＝6.3Hz,3H). 13 C NMR(125MHz,CDCl 3 ):δ67.6,62.4,36.1,28.9,23.3.
comparative example 1
The reaction temperature was changed to 60℃and the other steps were the same as in example 1. The product isolation yield was 58%.
Comparative example 2
The procedure of example 1 was followed except that the catalyst was changed to lithium t-butoxide. The product isolation yield was 72%.
Comparative example 3
The procedure of example 1 was followed without catalyst. The isolated yield of the product was 0.
Conclusion:
(1) As is evident from examples 1-6, the reaction was carried out at 80℃for 20h using lactone compound and pinacol borane as starting materials and toluene as solvent under LiHMDS catalysis, followed by addition of 2mol/L NaOH/MeOH solution and stirring at room temperature overnight. The separation yield of the diol product prepared by the method is higher than 86%, which shows that the catalytic addition of LiHMDS plays a very remarkable role in the reaction of preparing diol compounds from lactone compounds;
(2) Comparison of comparative example 1 and example 1 shows that: the reaction temperature plays a positive role in the reaction of preparing the diol compound from the lactone compound, and the reaction temperature is matched with parameters such as a catalyst, a reaction step, reaction raw materials and the like to form a reaction system in the invention; if the reaction is not carried out according to the reaction temperature in the present invention, the separation yield is directly reduced;
(3) As can be seen from comparison of comparative examples 2, 3 and example 1, other conditions were the same, and it was difficult to achieve the object of producing a diol compound from a lactone compound without adding a catalyst; and under other conditions, the separation yield of alcohol compounds prepared by changing the catalyst into other catalysts such as lithium tert-butoxide is lower than LiHMDS, so that the catalyst has remarkable progress.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents should be included in the scope of the claims of the present invention.

Claims (3)

1. A glycol synthesis method is characterized in that lithium bis (trimethylsilyl) amide is used as a catalyst, a compound shown in a formula I and a compound shown in a formula II are used as raw materials in 2mol/L NaOH/MeOH solution, and a compound shown in a formula III is prepared through a hydroboration reaction, wherein the chemical reaction equation is as follows:
in the above formula, formula I is various lactone compounds; formula II is pinacolborane; formula III is a diol;
R 1 is phenyl or alkyl.
2. The process for the synthesis of diols according to claim 1, wherein the compound of formula I, in molar ratio: a compound of formula II: catalyst = 1.0:2.0:0.08.
3. the method for synthesizing a diol according to claim 1, wherein the reaction temperature is 80℃and the reaction time is 20 hours.
CN202111297256.XA 2021-11-02 2021-11-02 Synthesis method of diol Active CN113880688B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111297256.XA CN113880688B (en) 2021-11-02 2021-11-02 Synthesis method of diol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111297256.XA CN113880688B (en) 2021-11-02 2021-11-02 Synthesis method of diol

Publications (2)

Publication Number Publication Date
CN113880688A CN113880688A (en) 2022-01-04
CN113880688B true CN113880688B (en) 2023-09-08

Family

ID=79016756

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111297256.XA Active CN113880688B (en) 2021-11-02 2021-11-02 Synthesis method of diol

Country Status (1)

Country Link
CN (1) CN113880688B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115872840A (en) * 2022-12-13 2023-03-31 汕头大学 Tetra-aryl pinacol derivative and synthesis method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276433A (en) * 2018-01-26 2018-07-13 南京林业大学 A kind of Hydroboronation process of ester
CN108610237A (en) * 2018-05-29 2018-10-02 复旦大学 A method of synthesis O-phthalic 01 derivatives
CN109369696A (en) * 2018-12-25 2019-02-22 苏州大学 It is the method for catalyst preparation alcoholic compound using anilino- lithium compound
CN113563372A (en) * 2021-08-31 2021-10-29 温州大学新材料与产业技术研究院 Synthesis method of alkenyl borate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276433A (en) * 2018-01-26 2018-07-13 南京林业大学 A kind of Hydroboronation process of ester
CN108610237A (en) * 2018-05-29 2018-10-02 复旦大学 A method of synthesis O-phthalic 01 derivatives
CN109369696A (en) * 2018-12-25 2019-02-22 苏州大学 It is the method for catalyst preparation alcoholic compound using anilino- lithium compound
CN113563372A (en) * 2021-08-31 2021-10-29 温州大学新材料与产业技术研究院 Synthesis method of alkenyl borate

Also Published As

Publication number Publication date
CN113880688A (en) 2022-01-04

Similar Documents

Publication Publication Date Title
CN106040303B (en) β-di-imidogen bivalent rare earth boron hydrogen complex is in catalysis ketone and the application in borine hydroboration
CN112979400A (en) Method for preparing 2-iodo aryl ether under action of alkali metal hydride
CN113880688B (en) Synthesis method of diol
CN114181191B (en) Synthesis method of cyclic sulfate
CN110698467A (en) Synthetic method of engagliflozin
CN112812091B (en) Synthetic method of cyclic carbonate
CN112358379B (en) Preparation method of optically pure S-shaped 1,1-bis- (4-fluorophenyl) -2-propanol
Taniguchi et al. Stereoselective reduction of α, β-epoxy ketones with sodium borohydride in the presence of calcium chloride or lanthanum chloride. A practical preparation of erythro-α, β-epoxy alcohols
CN112300072A (en) High-yield synthesis method of 5-iodoisoquinoline compounds
CN109535120B (en) Preparation method of 7-substituted-3, 4,4, 7-tetrahydrocyclobutane coumarin-5-ketone
CN112010881A (en) Alkenyl boron compound and preparation method and application thereof
CN101381356B (en) Preparation method of simvastatin
CN107540700A (en) The method for preparing borate using three fragrant oxygen rare earth compoundings
CN111018899B (en) Method for preparing 1, 1-boron alkyne compound by metal catalysis of terminal olefin
JPH03321B2 (en)
CN113996339A (en) Catalyst for preparing cyclic carbonate and preparation method of cyclic carbonate
CN111217847A (en) Thiosilane ligand, preparation method thereof and application thereof in aryl boronization catalytic reaction
CN113860990B (en) Alcohol synthesis method
CN115417766B (en) Synthesis method of 3-hydroxy-4, 5-dimethoxy benzoic acid tert-butyl ester
CN116120163B (en) Synthesis method of bevacizidine acid and intermediate thereof
WO2018000400A1 (en) Application of β-diimide bivalent rare earth borohydride complex for catalyzing hydroboration reaction between ketone and borane
CN114539305B (en) Method for preparing double bond organic compound by dearomatization of benzofuran
CN110857284B (en) Method for synthesizing N-methyl aliphatic amine
CN117720542A (en) Preparation method of adefovir intermediate GS-441524
JP5623099B2 (en) Method for producing N-oxycarbonyl- (2S) -oxycarbonyl- (5S) -phosphonylpyrrolidine derivative

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant