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Preparation method of symmetric 1,7-dicarbonyl compound

A dicarbonyl compound, symmetrical technology, applied in the direction of organic chemistry, can solve the problems of limited scope of application, poor tolerance of groups, etc.

Inactive Publication Date: 2013-07-24
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, this method has the problem of site selectivity, which limits its application (Gong, Y. D.; Tanaka, H.; Iwasawa, N.; Narasaka, K. Bull. Chem . Soc. Jpn. 1998, 71, 2181; Fuson, R. C.; Walker J. T. Org. Synth.1943, Coll. Vol. 2, 169)
[0006] These methods can be used to synthesize symmetrical 1,7-dicarbonyl compounds, but because of the catalysis or metal participation of base or Lewis acid, it is difficult to The tolerance of the group is not good, which limits the scope of application

Method used

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  • Preparation method of symmetric 1,7-dicarbonyl compound
  • Preparation method of symmetric 1,7-dicarbonyl compound

Examples

Experimental program
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Effect test

Embodiment 1

[0063] Dithiocarbonic acid O -Ethyl- S -(1,7-Diphenyl-1,7-dioxohept-4-yl)ester 3a preparation of

[0064] Dithiocarbonic acid O -Ethyl- S- Dissolve (2-phenyl-2-oxoethyl) ester (2.2 mmol) and methallyl sulfone (1 mmol) in 1.5 mL of 1,2-dichloroethane, vacuumize the system, and fill Nitrogen was added, the oil bath was heated to reflux, lauroyl peroxide (DLP) (5 mol % xanthate, 46 mg) was added, and then DLP (10 mol %, 92 mg) was added every 60 min until 45 mol% DLP was added . Continue the reflux reaction for 10 hrs, spin off the solvent, and the resulting crude product is separated by silica gel column chromatography (eluent petroleum ether: ethyl acetate = 15:1 to 8:1) to obtain dithiocarbonic acid O -Ethyl- S -(1,7-diphenyl-1,7-dioxohept-4-yl) ester, light yellow solid 325 mg, yield 81%, melting point 72-73 o c. 1 H NMR (CDCl 3 , 400 MHz) ( δ , ppm) 1.36 (t, J = 7.1 Hz, 3H, CH 3 ), 2.09 (dddd, J = 14.8, 8.9, 7.2, 6.5 Hz, 2H in 2CH 2 ), 2.31 (dddd, J = 14....

Embodiment 2

[0066] Dithiocarbonic acidO -Ethyl- S -[1,7-bis(4-methoxyphenyl)-1,7-dioxohept-4-yl]ester 3b preparation of

[0067] According to the method described in Example 1, with dithiocarbonic acid O -Ethyl- S -(2-p-methoxyphenyl-2-oxoethyl) ester and methallyl sulfone as raw materials to obtain dithiocarbonic acid O -Ethyl- S -[1,7-bis(4-methoxyphenyl)-1,7-dioxohept-4-yl]ester, white solid 360 mg, yield 78%, melting point 60-61 o c. 1 H NMR (CDCl 3 , 400 MHz) ( δ , ppm) 1.36 (t, J = 7.1 Hz, 3H, CH 3 ), 2.08 (dddd, J = 14.5, 8.5, 6.3, 6.0 Hz, 2H in 2CH 2 ), 2.27 (dddd, J = 14.5, 8.5, 6.7, 5.0 Hz, 2H in 2CH 2 ), 3.06~3.20 (m, 4H, 2CH 2 ), 3.86 (s, 6H, 2CH 3 ), 3.93 (tt, J = 8.5, 5.0 Hz, 1H, CH), 4.57 (q, J = 7.1 Hz, 2H, CH 2 ), 6.92 (d, J = 8.8 Hz, 4H, ArH), 7.94 (d, J = 8.8 Hz, 4H, ArH). 13 C NMR (CDCl 3 , 100 MHz) ( δ , ppm) 13.6, 29.0, 35.3, 50.8, 55.4, 69.9, 113.6, 129.8, 130.2, 163.4, 197.6, 213.9.

Embodiment 3

[0069] Dithiocarbonic acid O -Ethyl- S -(2,8-dioxononan-5-yl)ester 3c preparation of

[0070] According to the method described in Example 1, with dithiocarbonic acid O -Ethyl- S -(2-oxopropyl) ester and methallyl sulfone as raw materials to obtain dithiocarbonic acid O -Ethyl- S -(2,8-dioxononan-5-yl) ester, pale yellow liquid 199 mg, yield 72%. 1 H NMR (CDCl 3 , 400 MHz) ( δ , ppm) 1.43 (t, J = 7.1 Hz, 3H, CH 3 ), 1.83 (dddd, J = 14.7, 8.5, 7.7, 6.7 Hz, 2H in 2CH 2 ), 2.04 (dddd, J = 14.7, 8.5, 7.5, 5.0 Hz, 2H in 2CH 2 ), 2.14 (s, 6H, 2CH 3 ), 2.59 (ddd, J = 15.0, 7.7, 6.7 Hz, 2H in 2CH 2 ), 2.63 (dt, J = 15.0, 7.5 Hz, 2H in 2CH 2 ), 3.71 (tt, J = 8.5, 5.0 Hz, 1H, CH), 4.64 (q, J = 7.1 Hz, 2H, CH 2 ). 13 C NMR (CDCl 3 , 100 MHz) ( δ , ppm) 13.7, 28.2, 30.0, 40.5, 50.5, 70.1, 207.6, 214.1.

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Abstract

The invention discloses a preparation method of a symmetric 1,7-dicarbonyl compound. The preparation method comprises a step of implementing free radical reaction on dithiocarbonic acid O-alkyl-S-(2-carboxymethyl) ester and allyl sulfone, allyl sulfoxide, allyl sulfide or allyl mercaptan carboxylate to obtain corresponding symmetric 1,7-dicarbonyl xanthate. The preparation method is simple and easily available in raw materials, convenient to operate, and applicable to mass production. The prepared compound can be used as an important organic and pharmaceutical synthesis intermediate, and the like.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of symmetrical 1,7-dicarbonyl compounds. Background technique [0002] Symmetrical 1,7-dicarbonyl compounds are relatively common in nature and also exist in known drugs. For example, studies have found that this type of compound and its derivatives have anti-tumor and anti-cancer activities, have shown good activity in anti-thrombosis experiments, and are also potential drugs for neuroprotection (McDonald, R. W.; Bunjobpon, W.; Liu, T.; Fessler, S.; Pardo, O. E.; Freer, I. K. A.; Glaser, M.; Seckl, M. J.; Anti-Cancer Drug Design 2001, 16(6) , 261; Gannon, M.; McElhinney, R. S.; Kessel, D. P. Roy. Irish Acad. , B 1980, 80B , 107; Fliedner, L. J., Jr.; Myers, M. J.; Schor, J. M.; Pachter, I. J. J. Med. Chem. 1973, 16 , 749; Abdelhamid, R.; Luo, J.; VandeVrede, L.; Kundu, I.; Michalsen, B.; Litosh, V. A.; Schiefer, I. T.; Gherezg...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C329/16C07D263/24
Inventor 许家喜黄忠衍
Owner BEIJING UNIV OF CHEM TECH
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