CN103739532A - Sulfide derivatives and preparation method and application thereof - Google Patents
Sulfide derivatives and preparation method and application thereof Download PDFInfo
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- CN103739532A CN103739532A CN201410007665.5A CN201410007665A CN103739532A CN 103739532 A CN103739532 A CN 103739532A CN 201410007665 A CN201410007665 A CN 201410007665A CN 103739532 A CN103739532 A CN 103739532A
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- 0 *c(cc1)cc(C(O)=O)c1SSc(c(*)c1)ccc1[N+]([O-])=O Chemical compound *c(cc1)cc(C(O)=O)c1SSc(c(*)c1)ccc1[N+]([O-])=O 0.000 description 1
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Abstract
The invention relates to sulfide derivatives. The preparation method comprises the following steps: in a water system, by taking sodium sulphide and powdered sulfur as raw materials, carrying out heating reflux to synthesize a sodium disulfide aqueous solution; dropwise adding the prepared sodium disulfide solution to an alkaline aqueous solution of halogenated nitro benzoic acid; adjusting the pH of the system to about 3-4 after reacting for 5-20 hours; separating out sediments, washing and filtering, and drying to obtain the product. Design building of a target compound is based on a mechanism for measuring sulfydryl by virtue of Ellman reagent, novel photometric detection reagents are provided for identification and determination of sulfhydryl compounds, and the sulfide derivatives can be further applied to the fields of clinical medicine and biological chemistry.
Description
Technical field
The present invention relates to disulfide derivative, be specifically related to a kind of disulfide derivative and preparation method thereof, and the application of this disulfide derivative sulfhydryl compound in detecting solution.
Background technology
Sulfhydryl compound extensively exists in vivo in case cell is subject to oxidative damage. and particularly small molecules sulfhydryl compound, if halfcystine, homocysteine, gsh are again the important integral parts of some amino acid and proteins, and plays a part very important in organism physiological and pathological metabolic process.Halfcystine shortage can cause fat, Achromotrichia, liver cell damage etc.; In blood plasma, the high-caliber detection of homocysteine is again the important means of prevention and diagnosis cardiovascular and cerebrovascular diseases; Gsh can maintain the redox running balance of cell well, in the physiological processs such as growth of oxidative stress and cell, is taking on key player.So the concentration of sulfhydryl compound is significant in biochemical and clinical medicine in detection of biological system.
Nineteen fifty-nine, disulphide 5,5 '-dithio two (2-nitrobenzoic acid) abbreviation Ellman reagent is just used as luminosity reagent sulfhydryl compound has been carried out to effective mensuration, and sensitivity reaches 1.4 * 10
4lmol
-1cm
-1.Ellman reagent is still widely used at present.And its advantage of spectrophotometry is: convenient to operation, easily universal, be convenient to apply in common experiment, be the analytical procedure that has development prospect.The present invention is intended to the synthetic new curing reagent of design for this reason, for identification and the mensuration of sulfhydryl compound provides the photometric detection reagent that a class is new, and will effectively be applied to clinical medicine and biochemical field.
Summary of the invention
The object of the present invention is to provide the disulfide derivative that a class is new, its effect can be carried out effectively analyzing and measuring to sulfhydryl compound, is expected to be applied to biochemistry and clinical medicine fields.
Disulfide derivative provided by the invention, structural formula is as follows:
Wherein: R
1=H, R
2=NO
2, R=COOH; Or R
1=H, R
2=COOH, R=NO
2; Or R
1=COOH, R
2=NO
2, R=NO
2; Or R
1=NO
2, R
2=NO
2, R=COOH.
The synthetic method of described disulfide derivative, comprises the steps:
(1) in aqueous systems, take sodium sulphite and sulphur powder is raw material, reflux, the synthetic sodium disulfide aqueous solution; The mol ratio of described sodium sulphite and sulphur powder is 1 ﹕ 1.2～1.3; Described sodium sulphite and the mol ratio of water are 1 ﹕ 138～280;
(2) under 0～80 ℃ of temperature condition, by the mol ratio of sodium sulphite and halogenated nitrobenzene formic acid, be that 1 ﹕ 0.95～1.7 drips the sodium disulfide solution making in (1) in the alkaline aqueous solution of halogenated nitrobenzene formic acid, react after 5～20 hours, regulation system pH is about 3～4, separate out precipitation, washing and filtering, is dried to obtain product; In the alkaline aqueous solution of described halogenated nitrobenzene formic acid, in every ml water, be dissolved with halogenated nitrobenzene formic acid 10～100mmoL, pH=8～10; The structural formula of described halogenated nitrobenzene formic acid is:
wherein: R
1=H, R
2=NO
2, R=COOH; Or R
1=H, R
2=COOH, R=NO
2; Or R
1=COOH, R
2=NO
2, R=NO
2; Or R
1=NO
2, R
2=NO
2, R=COOH; X is Cl or Br.
Reaction equation is shown in following general formula:
Na
2S+S→Na
2S
2
(X=Cl in formula, or Br)
Compared with prior art, advantage of the present invention and effect:
(1) synthetic operation is simple, and raw materials used cheap and easy to get, productive rate is higher; Reaction is carried out again in aqueous systems, is typical environmental friendliness synthetic (green synthetic).(2) all there is obvious reaction with sulfhydryl compound.(3) sulfhydryl compound halfcystine and homocysteine are had to good detectivity, the sensitivity of reaction is suitable with Ellman reagent.
Accompanying drawing explanation
Fig. 1, Fig. 2 be respectively 4,4 '-dithio two (3-nitrobenzoic acids) IR and
1hNMR spectrogram
Fig. 3, Fig. 4 be respectively 2,2 '-dithio two (5-nitrobenzoic acids) IR and
1hNMR spectrogram
Fig. 5, Fig. 6 be respectively 2,2 ′ – dithio two (3,5 – dinitrobenzoic acids) IR and
1hNMR spectrogram
Fig. 7, Fig. 8 be respectively 4,4 ′ – dithio two (3,5 – dinitrobenzoic acids) IR and
1hNMR spectrogram
Embodiment
Embodiment 1:4,4 '-dithio two (3-nitrobenzoic acids) synthetic
By 4.0mmolNa
2s9H
2o is dissolved in 20mL water, adds 5.2mmol sulphur powder, and reflux to reaction solution is reddish-brown, and filtered while hot obtains Na
2s
2the aqueous solution.Then above-mentioned solution is added drop-wise in the alkaline aqueous solution of the 15mLpH=9 that is dissolved with the bromo-3-nitrobenzoic acid of 10mmol4-, control temperature between 65～80 ℃, react after 6 hours, cooling, regulate reaction solution pH to be about 4, place 2 hours, separate out deep yellow precipitation, suction filtration, washing, is dried to obtain buff powder product.Yield 66%, mp:172～174 ℃.IR（KBr,ν/cm
-1）：3100,2835,1701,1602,1539,1356,480.
1HNMR（300MHz,CDCl
3）δ/ppm：9.8（1H）,8.7（1H）,8.3（1H）,7.9（1H）.Elemental?analysis?calcd(%)for:C
14H
8O
8N
2S
2:C42.42,H2.020,N7.071:Found:C41.98,H2.091,N6.969.
Infrared and the nuclear magnetic spectrum of 4,4 '-dithio two (3-nitrobenzoic acid) is shown in Fig. 1 and Fig. 2.
Embodiment 2:2,2 '-dithio two (5-nitrobenzoic acids) synthetic
By 8.0mmolNa
2s9H
2o is dissolved in 20mL water, adds 10mmol sulphur powder, and reflux to reaction solution is reddish-brown, and filtered while hot obtains Na
2s
2the aqueous solution.Then above-mentioned solution is added drop-wise in the alkaline aqueous solution of the 15mLpH=10 that is dissolved with 10mmol2-chloro-5-nitrobenzoic acid, control temperature between 60～70 ℃, react after 5 hours, cooling, regulate reaction solution pH to be about 3, place 2 hours, separate out deep yellow precipitation, suction filtration, washing, is dried to obtain yellow powder product.Yield 75.5%, mp:243～245 ℃.IR（KBr,ν/cm
-1）：3100,2866,1697,1600,1570,1515.1350,480.
1HNMR（300MHz,CDCl
3）δ/ppm：9.9（1H）,8.8（1H）,8.4（1H）,7.6（1H）.Elemental?analysis?calcd(%)for:C
14H
8O
8N
2S
2:C42.42,H2.020,N7.071:Found:C42.53,H2.091,N6.976.
Infrared and the nuclear magnetic spectrum of 2,2 '-dithio two (5-nitrobenzoic acid) is shown in Fig. 3 and Fig. 4.
Embodiment 3:2,2 ′ – dithio two (3,5 – dinitrobenzoic acids) synthetic
By 5mmol Na
2s9H
2o is dissolved in 20mL water, adds 6.25mmol sulphur powder, and reflux to reaction solution is reddish-brown, and filtered while hot obtains Na
2s
2the aqueous solution.Then above-mentioned solution being added drop-wise to temperature is 2～5 ℃, is dissolved with in the alkaline aqueous solution of 2.05g2 – Lv – 3,5 – dinitrobenzoic acid 15mL pH=10, reacts after 7 hours, suction filtration, by filtrate pH regulator to 3 left and right, the yellow mercury oxide of separating out, suction filtration, dry, obtain product.After recrystallization, obtain sterling, yield is about 60%.mp：187.6～189.4℃。IR（KBr,ν/cm
-1）：3087.8,1610.5,1448.4,916.1,3000～2500,1701.1,1309.6,
1255.6，933.5,1537.2,1348.1,736.8,702.0,644.2.
1HNMR（300MHz,CDCl
3）δ/ppm:9.0（2H）,8.7（2H）.Elemental?analysis?calcd(%)for:C
14H
6O
12N
4S
2:C34.57,H1.24,N11.52；Found:
C34.44,H1.24,N11.44.
Infrared and the nuclear magnetic spectrum of 2,2 ′ – dithio two (3,5 – dinitrobenzoic acid) is shown in Fig. 5 and Fig. 6.
Embodiment 4:4,4 ′ – dithio two (3,5 – dinitrobenzoic acids) synthetic
By 2.1mmol Na
2s9H
2o is dissolved in 10mL water, adds 2.5mmol sulphur powder, and reflux to reaction solution is reddish-brown, and filtered while hot obtains Na
2s
2the aqueous solution.Then above-mentioned solution being added drop-wise to temperature is 0～6 ℃, be dissolved with 0.5g4-chloro-3,5 ?in the 15mL alkaline aqueous solution of dinitrobenzoic acid, react after 20 hours, standing, suction filtration, with distilled water wash, be dried to obtain deep yellow powder-product, yield reaches 85%, and fusing point is more than 300 ℃.IR（KBr,ν/cm
-1）：3500～2500,
1716,1610,1344,1271,1132,723.
1HNMR（300MHz,C
3D
6O）δ/ppm:9.194（4H.Elemental?analysis?calcd(%)for:C
14H
6O
12N
4S
2:C34.57,H1.24,N11.52；Found:C34.74,H1.28,N11.51.
Infrared and the nuclear magnetic spectrum of 4,4 ′ – dithio two (3,5 – dinitrobenzoic acid) is shown in Fig. 7 and Fig. 8.
Embodiment 5:4, the reactivity worth of 4 '-dithio two (3-nitrobenzoic acid) and sulfhydryl compound (take halfcystine Cys as example)
Accurately draw 5 * 10
-4molL
-1cys solution 0.00,0.20,0.40,0.60,0.80,1.00mL respectively in 0-5 colorimetric cylinder, then add respectively successively 2.00mL borax buffer solution (pH9.1) and 6.00mL5 * 10
-4molL
-1two (3-nitrobenzoic acid) solution of 4,4 '-dithio, with distilled water, be settled to 10mL, color reaction 15 minutes, the blank reagent solution (No. 0 solution) of take is reference, with on UV2602 spectrophotometer, measures the absorbance of 1-5 solution at 310nm place.The sexual intercourse of result display line is good, r
2=0.998; Sensitivity e=1.1 * 10
4lmol
-1cm
-1.
Embodiment 6:2, the reactivity worth of 2 '-dithio two (5-nitrobenzoic acid) and Cys
Accurately draw 5 * 10
-4molL
-1cys solution 0.00,0.20,0.40,0.60,0.80,1.00mL respectively in 0-5 colorimetric cylinder, then add respectively successively 2.00mL borax buffer solution (pH9.1) and 5.00mL5 * 10
-4molL
-1two (5-nitrobenzoic acid) solution of 2,2 '-dithio, with distilled water, be settled to 10mL, color reaction 20 minutes, the blank reagent solution (No. 0 solution) of take is reference, with on UV2602 spectrophotometer, measures the absorbance of 1-5 solution at 425nm place.The sexual intercourse of result display line is good, r
2=0.9963; Sensitivity e=8.0 * 10
3lmol
-1cm
-1.
Embodiment 7:2, the reactivity worth of 2 ′ – dithio two (3,5 – dinitrobenzoic acid) and Cys
Accurately draw 1 * 10
-3molL
-1cys solution 0.00,0.10,0.20,0.30,0.40,0.50mL respectively in 0-5 colorimetric cylinder, then add respectively successively 2.00mL sodium carbonate sodium hydroxide buffer solution (pH10) and 2.00mL4 * 10
-4molL
-1two (3, the 5 – dinitrobenzoic acid) solution of 2,2 ′ – dithio, with distilled water, be settled to 10mL, color reaction 10 minutes, the blank reagent solution (No. 0 solution) of take is reference, with on UV2602 spectrophotometer, at 290nm place, measure the absorbance of 1-5 solution.The sexual intercourse of result display line is good, r
2=0.9947; Sensitivity e=9.6 * 10
3lmol
-1cm
-1.
Embodiment 8:4, the reactivity worth of 4 ′ – dithio two (3,5 – dinitrobenzoic acid) and Cys
Accurately draw 1 * 10
-3molL
-1cys solution 0.00,0.20,0.40,0.60,0.80,1.0mL respectively in 0-5 colorimetric cylinder, then add respectively successively 2.00mL sodium carbonate sodium hydroxide buffer solution (pH10) and 1.1mL7.5 * 10
-4molL
-1two (3, the 5 – dinitrobenzoic acid) solution of 4,4 ′ – dithio, with distilled water, be settled to 10mL, color reaction 8 minutes, the blank reagent solution (No. 0 solution) of take is reference, with on UV2602 spectrophotometer, at 250nm place, measure the absorbance of 1-5 solution.The sexual intercourse of result display line is good, r
2=0.9974; Sensitivity e=7.4 * 10
3lmol
-1cm
-1.
Claims (3)
1. a disulfide derivative, is characterized in that, structural formula is:
Wherein: R
1=H, R
2=NO
2, R=COOH; Or R
1=H, R
2=COOH, R=NO
2; Or R
1=COOH, R
2=NO
2, R=NO
2; Or R
1=NO
2, R
2=NO
2, R=COOH.
2. the synthetic method of a kind of disulfide derivative as claimed in claim 1, is characterized in that, comprises the steps:
(1) in aqueous systems, take sodium sulphite and sulphur powder is raw material, reflux, the synthetic sodium disulfide aqueous solution; The mol ratio of described sodium sulphite and sulphur powder is 1 ﹕ 1.2～1.3; Described sodium sulphite and the mol ratio of water are 1 ﹕ 138～280;
(2) under 0-80 ℃ of temperature condition, by the mol ratio of sodium sulphite and halogenated nitrobenzene formic acid, be that 1 ﹕ 0.95～1.7 drips the sodium disulfide solution making in (1) in the alkaline aqueous solution of halogenated nitrobenzene formic acid, react after 5～20 hours, regulation system pH is about 3～4, separate out precipitation, washing and filtering, is dried to obtain product; In the alkaline aqueous solution of described halogenated nitrobenzene formic acid, in every ml water, be dissolved with halogenated nitrobenzene formic acid 10～100mmoL, pH=8～10; The structural formula of described halogenated nitrobenzene formic acid is:
wherein: R
1=H, R
2=NO
2, R=COOH; Or R
1=H, R
2=COOH, R=NO
2; Or R
1=COOH, R
2=NO
2, R=NO
2; Or R
1=NO
2, R
2=NO
2, R=COOH; X is Cl or Br.
3. the application of a kind of disulfide derivative as claimed in claim 1 sulfhydryl compound in detecting solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467525A (en) * | 2017-12-31 | 2019-03-15 | 苏州亚科科技股份有限公司 | A kind of DTNB total synthesis method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3119668A (en) * | 1959-01-26 | 1964-01-28 | Dow Chemical Co | Sulfhydryl tests and compounds therefor |
| US3756976A (en) * | 1971-04-28 | 1973-09-04 | Phillips Petroleum Co | Production of odor-free polymer latex |
| CN1103865A (en) * | 1993-12-13 | 1995-06-21 | 大连化工助剂厂 | Method for prodn. of dibenzyl disulfide |
-
2014
- 2014-01-08 CN CN201410007665.5A patent/CN103739532B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3119668A (en) * | 1959-01-26 | 1964-01-28 | Dow Chemical Co | Sulfhydryl tests and compounds therefor |
| US3756976A (en) * | 1971-04-28 | 1973-09-04 | Phillips Petroleum Co | Production of odor-free polymer latex |
| CN1103865A (en) * | 1993-12-13 | 1995-06-21 | 大连化工助剂厂 | Method for prodn. of dibenzyl disulfide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467525A (en) * | 2017-12-31 | 2019-03-15 | 苏州亚科科技股份有限公司 | A kind of DTNB total synthesis method |
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