Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

4,4'-dimercaprol azobenzene and preparation method thereof

A technology of dimercaptoazo and diiodoazobenzene, applied in 4 fields, can solve the problems of poor reaction selectivity, high toxicity of reagents, low yield and the like, and achieve the effect of mild reaction conditions

Inactive Publication Date: 2013-03-20
XIAMEN UNIV
View PDF1 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

All there are shortcomings such as low yield, high reagent toxicity, high unit consumption, poor reaction selectivity (references: L.R.Sita etc., Tetrahedron Letter, 1995,36,4525-4528 in direct synthesis; M.A.Reed, J.M.Tour etc., Tetrahedron , 2003, 59, 8555-8570)

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
  • 4,4'-dimercaprol azobenzene and preparation method thereof
  • 4,4'-dimercaprol azobenzene and preparation method thereof
  • 4,4'-dimercaprol azobenzene and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] (1) Preparation of 4-iodoaniline (2)

[0042] Add NaHCO to a 1L round bottom flask 3 (15.16g, 180mmol) and water (250mL), after completely dissolving, add aniline (11.18g, 10.94mL, 120mmol), add ice cubes to cool the solution to 12-15°C, add I in batches within 15min under vigorous stirring 2 (25.38g, 100mmol), suction filtration after 30min reaction, the dark gray solid crude product can be obtained by saturated NaHSO 3 Decolorization, sublimation at 40 ° C after drying in the air to give 4-iodoaniline (2).

[0043] Yield: 16.4 g, 75%.

[0044] Physical properties: white needle-like crystals; melting point (M.p.) is 66°C; molecular formula I-C 6 h 4 -NH 2 ; Molecular weight 219.02; Soluble in any organic solvent.

[0045] Spectroscopy data:

[0046] 1 H NMR (400MHz, CDCl 3 , 298K, ppm): δ7.39(d, 3 J H，H =8.8Hz, 2H), 6.46(d, 3 J H，H =8.8Hz, 2H), 3.477(s, 2H).

[0047] 13 C NMR (100MHz, CDCl 3 , 298K, ppm): δ147.1, 138.2, 115.9, 80.1.

[0048] IR (KBr, c...

Embodiment 2

[0074] Similar to Example 1, the difference is that the solvent in the preparation of 4-iodoaniline (2) is dioxane and pyridine. The specific steps are: in a 1L round-bottomed flask, add aniline (9.31g, 9.12mL, 100mmol), dioxane (150mL) and pyridine (100mL), cooled to about 0°C in an ice bath, and quickly added I 2 (50.76g, 200mmol), the solution gradually turned reddish brown. After 1h, remove the ice bath, continue to stir at room temperature for 3h, add Na 2 S 2 o 3 Saturate the solution until the solution is brownish red and clear, then use CH 2 Cl 2 (150mL×2) extraction, the combined organic layers were washed with anhydrous Na 2 SO 4 After drying, the solvent was drained to a dark red solid, which was sublimed at 40°C to obtain 4-iodoaniline (2) (14.85 g, 68%) in the form of white needles.

Embodiment 3

[0076] Similar to Example 1, the difference is that KMnO is used for oxidative coupling 4 、CuSO 4 ·5H 2 O and Al 2 o 3 Supported oxidation system, the specific steps are: 6.321g (40mmol) KMnO 4 Dissolve in water to form a concentrated solution, add 15g of 200-300 mesh Al 2 o 3 Put the powder in a 250mL round-bottomed flask, stir well to form a slurry. Then weigh 9.98g (40mmol) CuSO 4 ·5H 2 O, fully pulverized with a mortar and added to the above slurry, stirred evenly, added 2.19g (10mmol) 4-iodoaniline (2) at one time, mechanically stirred for 24h, followed by TLC until the reaction was complete. The obtained purple-black solid was treated with 10 mL×3 CH 2 Cl 2 Extract and filter to obtain an orange-red solution. The obtained orange-red solution was heated to evaporate part of the solvent and then cooled to obtain orange-red flaky crystal 4,4'-diiodoazobenzene (3) (0.98g, 45%).

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

PropertyMeasurementUnit
melting pointaaaaaaaaaa
melting pointaaaaaaaaaa
Login to View More

Abstract

The invention discloses 4,4'-dimercaprol azobenzene and a preparation method thereof and relates to an azo sulfhydryl compound. The molecular formula of the 4,4'-dimercaprol azobenzene is HS(C6H4)N=N(C6H4)SH. The method comprises the following steps of: dissolving aniline into an aqueous sodium bicarbonate solution; adding I2 for reacting, then decompressing and pumping off the solvent to obtain 4-m-iodoaniline; dissolving the 4-m-iodoaniline into glacial acetic acid, adding NaBO3-4H2O and H3BOs for reacting, and then recrystallizing by using THF (Tetrahydrofuran) to obtain 4,4'-azobenzene diiodide; dissolving the 4,4'-azobenzene diiodide into the THF, adding an obtained mixed solution to magnesium chips in batches, and then cooling to obtain an azobenzene Grignard reagent; adding solid sulphur powder to the azobenzene Grignard reagent in batches and heating for reacting to obtain a vulcanized product; cooling and then adding an NH4Cl solution; acidizing by using hydrochloric acid and extracting through dichloromethane; combining organic phases, drying and filtering; decompressing to evaporate out the solvent to obtain a crude product; and extracting by using alcohol, and evaporating the solvent to dryness to obtain a product.

Description

technical field [0001] The invention relates to an azo mercapto compound, in particular to 4,4'-dimercaptoazobenzene with cheap and easy-to-obtain starting materials, high yield and purity, simple process and a preparation method thereof. Background technique [0002] As potential microelectronic materials, azo-mercapto compounds have been used in the research fields of electrochemistry and surface chemistry; at the same time, they can also be used as a special free radical initiator, which can initiate the polymerization of various olefin molecules. At present, there are still many difficulties in synthesizing this type of compound, especially the higher product of purity, mainly including: (1) the oxidation preparation of its reaction precursor 4,4'-diiodoazobenzene, the yield is not high, Product is difficult to separate; (2) the direct preparation of mercapto group is difficult, often needs acyl protection and deprotection, so undoubtedly improves the preparation cost of...

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): C07C323/48C07C319/02
Inventor 朱红平郑治尧王娟娟任斌黄奕凡吴德印
Owner XIAMEN UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com