Unlock instant, AI-driven research and patent intelligence for your innovation.

Preparation methods of acids with different substituents

A technology of substituents and hydrocarbon groups, applied in the field of organic synthesis, can solve the problems of complicated operation, poor safety, harsh conditions, etc., and achieve the effects of high atom economy, wide application range of substrates and simple operation.

Active Publication Date: 2020-07-10
HUNAN UNIV
View PDF3 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The above several methods all have raw materials that are easy to get and high yield, but the disadvantage is that the cost of the sodium cyanide method is high, and the used raw material sodium cyanide is a highly toxic article, which has poor safety and will cause environmental pollution. The high cost; catalytic thermal decarboxylation synthesis requires harsh conditions, cumbersome operation and low yield; the chloride carbonylation method uses highly toxic carbon monoxide as raw material, high pressure conditions increase operational risks, and transition metal catalysis is required

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Preparation methods of acids with different substituents
  • Preparation methods of acids with different substituents
  • Preparation methods of acids with different substituents

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] At -78°C, n-butyllithium (2.4mL, 2.5mol / L, 1.2eq) was added dropwise to a tetrahydrofuran solution (15mL) of cyclopropyne (330.5mg, 1.0eq) to react for 1h, and then isopropyl Alcohol pinacol borate (1.2mL, 1.2eq) was added dropwise to the mixed solution, the reaction was continued for 2h, and hydrogen chloride solution in 1,4-dioxane (1.9mL, 4M in dioxane, 1.5eq) was added to quench , the reaction was raised to room temperature, and after the solvent was rotatably evaporated, it was formulated into an acetone solution (0.3M), and then potassium peroxymonosulfonate solution (0.5M, 4.6107g, 1.5 equivalents) was added, transferred to 50°C and stirred for 12h, separated After purification, 475.6 mg of cyclopropaneacetic acid with a purity of 95% was obtained.

[0035] The hydrogen spectrum and carbon spectrum data are as follows:

[0036] 1 H NMR (400MHz, CDCl 3 )δ10.98(br s,1H),2.25(d,J=7.1Hz,2H),1.10–0.98(m,1H),0.55(d,J=8.6Hz,2H),0.17(d,J= 5.0Hz, 2H);

[0037] 13 C ...

Embodiment 2

[0039]At -78°C, n-butyllithium (2.4mL, 2.5mol / L, 1.2eq) was added dropwise to a solution of 1-octyne (551.0mg, 1.0eq) in tetrahydrofuran (15mL) for 1h, and then iso Propanol pinacol borate (1.2mL, 1.2eq) was added dropwise to the mixed solution, the reaction was continued for 2h, and hydrogen chloride solution in 1,4-dioxane (1.9mL, 4M in dioxane, 1.5eq) was added to quench After the reaction was extinguished, the reaction was raised to room temperature, and the solvent was rotary evaporated to form an acetone solution (0.3M), then potassium peroxymonosulfonate solution (0.5M, 4.6107g, 1.5 equivalents) was added, and transferred to 50°C and stirred for 12h. After separation and purification, 612.9 mg of octanoic acid with a purity of 85% was obtained.

[0040] The hydrogen spectrum and carbon spectrum data are as follows:

[0041] 1 H NMR (400MHz, CDCl 3 )δ10.95(br s,1H),2.34(t,J=7.5Hz,2H),1.70–1.58(m,2H),1.36–1.23(m,8H),0.88(t,J=6.8Hz, 3H);

[0042] 13 C NMR (101MHz, CD...

Embodiment 3

[0044] At -78°C, n-butyllithium (2.4mL, 2.5mol / L, 1.2eq) was added dropwise to a tetrahydrofuran solution (15mL) of 4-methylphenylacetylene (580.8mg, 1.0eq) to react for 1h, and then Isopropanol pinacol borate (1.2mL, 1.2eq) was added dropwise to the mixed solution, the reaction was continued for 2h, and a solution of hydrogen chloride in 1,4-dioxane (1.9mL, 4M indioxane, 1.5eq) was added After quenching, the reaction was raised to room temperature, and the solvent was evaporated to form an acetone solution (0.3M), then potassium peroxymonosulfonate solution (0.5M, 4.6107g, 1.5 equivalents) was added, and the mixture was transferred to 50°C and stirred for 12h , separated and purified to obtain 555.7 mg of 4-methylphenylacetic acid with a purity of 74%.

[0045] The hydrogen spectrum and carbon spectrum data are as follows:

[0046] 1 H NMR (400MHz, CDCl 3 )δ10.75(br s,1H),7.19(q,J=8.2Hz,4H),3.64(s,2H),2.37(s,3H);

[0047] 13 C NMR (101MHz, CDCl 3 ) δ 178.52, 137.11, 130...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a preparation method of an acid with different substituent groups. A terminal alkyne is lithiated with n-butyllithium, and then reacts with isopropoxyboronic acid pinacol ester, hydrogen chloride is added to achieve quenching, then the obtained reaction product is oxidized by an oxidizing agent, and the oxidized reaction product is separated and purified to obtain the acid.The method of the invention has the advantages of simplicity in operation, one-pot process preparation, no metal catalysis, nontoxic reagents, greenness, environmental friendliness and high atomic utilization rate, and provides a novel and quick way for preparing the acid with different substituent groups; and the obtained acid is an important fine chemical product, and can be widely used in fields of medicines, pesticides, spices and other industries.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to the preparation method of acids with different substituents. Specifically, the preparation method uses terminal alkynes, n-butyllithium, isopropanol pinacol borate, hydrogen chloride and peroxide Potassium monosulfonate was used as starting material to obtain the corresponding acid by one-pot method. Background technique [0002] As a very important fine chemical, acids with different substituents are widely used in pharmaceutical, pesticide and fragrance industries. [0003] In terms of fine chemicals, acids with different substituents are important chemical experiment substrates, that is, important intermediates for the synthesis of esters and amides, and important substrates for reduction into alcohols and aldehydes, playing a vital role. [0004] In medicine, acids with different substituents are the synthetic hypnotic drug luminal, the drug azelastine for the treatm...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07C51/00C07C53/134C07C53/126C07C57/30C07C57/34C07C57/50C07C57/58C07C253/30C07C255/57C07C255/19C07C53/19C07C57/32C07C57/40C07C59/64C07D307/87
CPCC07C51/00C07C59/64C07C253/30C07C2601/02C07C2603/24C07D307/87C07C53/134C07C53/126C07C57/30C07C57/34C07C57/50C07C57/58C07C53/19C07C57/32C07C57/40C07C255/57C07C255/19
Inventor 赵万祥李若玲李晨晨赵珮
Owner HUNAN UNIV