CN103288693A - Method for preparing 1-thiol pyrene and intermediate compound thereof - Google Patents
Method for preparing 1-thiol pyrene and intermediate compound thereof Download PDFInfo
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Abstract
The invention relates to a method for preparing 1-thiol pyrene and an intermediate compound thereof, belonging to preparation methods of thiol compound intermediates. The method comprises the following steps of: (1) synthesizing a 1-thiol pyrene intermediate namely O-1-pyrenyl dimethylamino sulfo-formate: adding 1-hydroxy pyrene and sodium hydride into a solvent namely N,N-dimethylfomamide to react, adding dimethylamino sulfo-formyl chloride to react, adding an appropriate amount of solid potassium carbonate to react, and treating to obtain a yellow 1-thiol pyrene intermediate namely O-1-pyrenyl dimethylamino sulfo-formate; (2) synthesizing a 1-thiol pyrene intermediate namely S-1-pyrenyl dimethylamino sulfo-formate: performing a rearrangement reaction on the O-1-pyrenyl dimethylamino sulfo-formate, and then purifying to obtain a khaki 1-thiol pyrene intermediate namely S-1-pyrenyl dimethylamino sulfo-formate; and (3) synthesizing 1-thiol pyrene: adding potassium hydroxide into a solvent namely a mixed solution including water and glycol, then adding the S-1-pyrenyl dimethylamino sulfo-formate to perform hydrolysis, and neutralizing with dilute hydrochloric acid of which the mass fraction is 5% to obtain yellow 1-thiol pyrene.
Description
Technical field
The present invention relates to a kind of thin based compound intermediates preparation, be specifically related to the synthetic method of a kind of 1-of preparation sulfydryl pyrene and midbody compound thereof.
Background technology
Dredging the of many uses of based compound, is important chemical material and important medicine intermediate, can be used as the intermediate of medicine, agricultural chemicals and weedicide, can cook toxinicide, thiofide.Sulfydryl is very strong nucleophilic group, can be used as the important functional group of organic reaction.In addition, sulfydryl can have very strong complexing action with some heavy metal ion.The pyrenyl compound is widely used in photoelectric functional material and bio-science fields such as molecular probe, Organic Light Emitting Diode, organic solar batteries simultaneously.Therefore, the sulfydryl pyrene has extensively important purposes in field of new such as molecule photoelectric functional material and bioprobe materials.But at present, the sulfydryl pyrene is not commercial distribution as yet at home and abroad, mainly is to lack simple and effective synthetic method.
Summary of the invention
The objective of the invention is to provide the synthetic method of a kind of 1-of preparation sulfydryl pyrene and midbody compound thereof, solve the composition problem that the sulfydryl pyrene can not be simple and effective.
The object of the present invention is achieved like this: at first synthetic 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic, utilize rearrangement reaction then, and generate 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic, hydrolysis forms 1-sulfydryl pyrene again.
The reaction formula of described 1-sulfydryl pyrene and 1-sulfydryl pyrene midbody compound is expressed as follows:
Concrete grammar is as follows:
Synthesizing of 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic:
Under nitrogen protection, 1-hydroxyl pyrene is dissolved in N, and dinethylformamide (DMF) is cooled to 0～5 ℃, slowly adds massfraction and be 60% sodium hydride, stirring reaction 30 minutes; Add dimethylamino sulfo-formyl chloride (DMTCC), be warming up to 80 ℃; Add an amount of salt of wormwood again, continue reaction 30 hours, unreacted salt of wormwood is filtered in cooling; Add big water gaging, produce yellow mercury oxide, filter, recrystallizing methanol gets yellow 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic, and yield is 98.0%.
Molecular structure and the crystalline structure of 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic:
These compound crystal data, crystallographic system: monocline; Spacer: P2
1Molecular formula: C
19H
15ONS; Molecular weight: 305.38; Unit cell parameters:
α=90.00 °,
γ=90.00 °; Unit cell volume:
Temperature: 296 (2) K; Structure cell density: 1.344g cm
– 3Structure factor (F (000)): 1280; Absorption factor: 0.215mm
– 1Can observe S value (the GOF on F of point diffraction
2): 1.021; The factor [I〉2sigma (I)]: R as a result
1=0.0774, wR
2=0.1020.137～139 ℃ of fusing points.
Synthesizing of 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic:
The O-1-pyrenyl dimethylamino thiocarboxylic of drying crystalline attitude is joined in the stainless steel cauldron; exist or the disappearance solvent; under the nitrogen protection condition; temperature rises to 260～290 ℃ fast; reacted 45～100 minutes; get 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic through column chromatography for separation, yield is 40.0～87.2%.
Molecular structure and the crystalline structure of 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic:
These compound crystal data, crystallographic system: quadrature; Spacer: Pbca; Molecular formula: C
19H
15ONS; Molecular weight: 305.38; Unit cell parameters: unit cell parameters:
α=90.00 °, β=90.00 °, γ=90.00 °; Unit cell volume:
Temperature: 123 (2) K; Structure cell density: 1.363g cm
– 3Structure factor (F (000)): 2560; Absorption factor: 0.218mm
– 1Can observe S value (the GOF on F of point diffraction
2): 0.957; The factor [I〉2sigma (I)]: R as a result
1=0.0690, wR
2=0.1077.131～134 ℃ of fusing points.
Synthesizing of 1-sulfydryl pyrene:
Under nitrogen protection, in the mixing solutions (1:7 volume ratio) of water and ethylene glycol, add potassium hydroxide, add S-pyrene-1-base dimethylamino metilsulfate again, refluxed 1.5 hours; After the cooling, in reaction soln impouring frozen water, add the chloroform vibration fully, discard chloroform layer, water layer is used chloroform extraction again with the careful acidifying of dilute hydrochloric acid of massfraction 5%, obtains yellow 1-sulfydryl pyrene behind the evaporate to dryness, and yield is 86.5%.
1-sulfydryl pyrene contains pyrenyl luminophore and mercapto functional group, and molecular structure is as follows:
86～89 ℃ of fusing points.
Beneficial effect, owing to adopted such scheme, 1-sulfydryl pyrene is synthetic easier, simple to operate, yield height (full yield can reach 73.9%) can be used for prepared in laboratory and fairly large production.At first utilize the synthetic O-1-pyrenyl dimethylamino thiocarboxylic of the high yield of simple nucleophilic substitution reaction; Next utilizes famous Newman-Kwart rearrangement reaction to synthesize S-1-pyrenyl dimethylamino thiocarboxylic; At last synthesized 1-sulfydryl pyrene based on traditional hydrolysis reaction.
Advantage: it is few to adopt the synthetic 1-sulfydryl pyrene of this programme and intermediate thereof to have a side reaction, the yield height, and separation and purification easily, the reaction times is short, and operation is simple, advantages such as scalable large-scale production.In addition, can be used for synthetic 2-sulfydryl pyrene and 4-sulfydryl pyrene fully.
Description of drawings
Fig. 1 is reaction equation figure of the present invention.
Embodiment
Below by example in detail the present invention is described in detail, yet, the invention is not restricted to following embodiment.
The at first synthetic 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic of embodiment 1 utilizes rearrangement reaction then, generates 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic, and hydrolysis forms 1-sulfydryl pyrene again.
The reaction formula of described 1-sulfydryl pyrene and 1-sulfydryl pyrene midbody compound is expressed as follows:
Concrete grammar is as follows:
Synthesizing of 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic:
Under nitrogen protection, 1-hydroxyl pyrene is dissolved in N, and dinethylformamide (DMF) is cooled to 0～5 ℃, slowly adds massfraction and be 60% sodium hydride, stirring reaction 30 minutes; Add dimethylamino sulfo-formyl chloride (DMTCC), be warming up to 80 ℃; Add an amount of salt of wormwood again, continue reaction 30 hours, unreacted salt of wormwood is filtered in cooling; Add big water gaging, produce yellow mercury oxide, filter, recrystallizing methanol gets yellow 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic, and yield is 98.0%.
Molecular structure and the crystalline structure of 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic:
These compound crystal data, crystallographic system: monocline; Spacer: P2
1Molecular formula: C
19H
15ONS; Molecular weight: 305.38; Unit cell parameters:
α=90.00 °, β=90.702 (4) °, γ=90.00 °; Unit cell volume:
Temperature: 296 (2) K; Structure cell density: 1.344g cm
– 3Structure factor (F (000)): 1280; Absorption factor: 0.215mm
– 1Can observe S value (the GOF on F of point diffraction
2): 1.021; The factor [I〉2sigma (I)]: R as a result
1=0.0774, wR
2=0.1020.137～139 ℃ of fusing points.
Synthesizing of 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic:
The O-1-pyrenyl dimethylamino thiocarboxylic of drying crystalline attitude is joined in the stainless steel cauldron; exist or the disappearance solvent; under the nitrogen protection condition; temperature rises to 260～290 ℃ fast; reacted 45～100 minutes; get 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic through column chromatography for separation, yield is 40.0～87.2%.
Molecular structure and the crystalline structure of 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic:
These compound crystal data, crystallographic system: quadrature; Spacer: Pbca; Molecular formula: C
19H
15ONS; Molecular weight: 305.38; Unit cell parameters: unit cell parameters:
α=90.00 °, β=90.00 °, γ=90.00 °; Unit cell volume:
Temperature: 123 (2) K; Structure cell density: 1.363g cm
– 3Structure factor (F (000)): 2560; Absorption factor: 0.218mm
– 1Can observe S value (the GOF on F of point diffraction
2): 0.957; The factor [I〉2sigma (I)]: R as a result
1=0.0690, wR
2=0.1077.131～134 ℃ of fusing points.
Synthesizing of 1-sulfydryl pyrene:
Under nitrogen protection, in the mixing solutions (1:7 volume ratio) of water and ethylene glycol, add potassium hydroxide, add S-1-pyrenyl dimethylamino thiocarboxylic again, refluxed 1.5 hours; After the cooling, in reaction soln impouring frozen water, add the chloroform vibration fully, discard chloroform layer, water layer is used chloroform extraction again with the careful acidifying of dilute hydrochloric acid of massfraction 5%, obtains yellow 1-sulfydryl pyrene behind the evaporate to dryness, and yield is 86.5%.
1-sulfydryl pyrene contains pyrenyl luminophore and mercapto functional group, and molecular structure is as follows:
86～89 ℃ of fusing points.
Embodiment 2:
1,1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic is synthetic:
Under nitrogen protection, 6.54 gram 1-hydroxyl pyrenes are dissolved in 50 milliliters of N, dinethylformamide (DMF), be cooled to 0～5 ℃, slowly add 2.40 gram mass marks and be 60% sodium hydride, stirring reaction 30 minutes, add 6.00 gram dimethylamino sulfo-formyl chlorides (DMTCC), slowly be warming up to 80 ℃; Add 3.25 gram salt of wormwood again, continue reaction 30 hours; Unreacted salt of wormwood is filtered in cooling; Add 100 ml distilled waters, produce yellow mercury oxide, filter, recrystallizing methanol obtains yellow 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic, and yield is 98.0%.
Its structural characterization data are as follows:
Infrared spectra: KBr, ν (cm
-1): 3038.89 (Ar-H), 2933.05 (C – H), 1530.38 (s, C=C), 1231.24 (C – O), 1130.43 (s, C=S).
Mass spectroscopy: m/z (%): 305 (30, M
+), 189 (30), 88 (10), 72 (100).
Nuclear magnetic data:
1H-NMR (CDC1
3) (400MHz), δ 3.482-3.689 (6H, t, N-CH
3), 7.753-8.181 (9H, m, Ar).
The main crystal data of this compound.Crystallographic system: monocline; Spacer: P2
1Molecular formula: C
19H
15ONS; Molecular weight: 305.38; Unit cell parameters:
α=90.00 °, β=90.702 (4) °, γ=90.00 °; Unit cell volume:
Temperature: 296 (2) K; Structure cell density: 1.344g cm
– 3Structure factor (F (000)): 1280; Absorption factor: 0.215mm
– 1Can observe S value (the GOF on F of point diffraction
2): 1.021; The factor [I〉2sigma (I)]: R as a result
1=0.0774, wR
2=0.1020; 137～139 ℃ of fusing points.
Feature bond distance's bond angle: bond distance
C
Virtue– O, 1.401 (5); C – O, 1.362 (4); C=S:1.657 (4); Bond angle (°): C
Virtue– O – C, 118.6 (3); O – C – N, 110.3 (3); O – C=S, 123.7 (3); N – C=S, 126.0 (3).
2,1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic is synthetic:
4.0 gram O-1-pyrenyl dimethylamino thiocarboxylics drying, crystal form are joined in the stainless steel cauldron; under the nitrogen protection condition; temperature rises to 290 ℃ fast; reacted 1 hour; get 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic through column chromatography (methylene dichloride: sherwood oil=2.5:1(volume ratio)), yield is 76.5%.
Infrared spectra: KBr, ν (cm
-1) 3038.89 (Ar-H), 2933.05 (C – H), 1165.95 (s, C=O), 688.67 (C – S).
Mass spectroscopy: m/z (%): 305 (30, M
+, 189 (25), 88 (10), 72 (100).
Nuclear magnetic data:
1H-NMR (CDCl
3) (400MHz), δ 3.050-3.306 (6H, t, N-CH
3), 8.013-8.583 (9H, m, Ar).
The main crystal data of this compound.Crystallographic system: quadrature; Spacer: Pbca; Molecular formula: C
19H
15ONS; Molecular weight: 305.38; Unit cell parameters: unit cell parameters:
α=90.00 °, β=90.00 °, γ=90.00 °; Unit cell volume:
Temperature: 123 (2) K; Structure cell density: 1.363g cm
– 3Structure factor (F (000)): 2560; Absorption factor: 0.218mm
– 1Can observe S value (the GOF on F of point diffraction
2): 0.957; The factor [I〉2sigma (I)]: R as a result
1=0.0690, wR
2=0.1077; 131～134 ℃ of fusing points.
Feature bond distance's bond angle: bond distance
C
Virtue– S, 1.781 (3); C – S, 1.816 (3); C=O:1.231 (3); Bond angle (°): C
Virtue– S – C, 102.79 (15); O=C – N, 124.6 (2); O=C – S, 122.19 (18); N – C – S, 113.1 (2).
3,1-sulfydryl pyrene is synthetic: under nitrogen protection, add potassium hydroxide in the mixing solutions (1:7 volume ratio) of water and ethylene glycol, add S-1-pyrenyl dimethylamino thiocarboxylic again, refluxed 1.5 hours; After the cooling, in reaction soln impouring frozen water, add the chloroform vibration fully, discard chloroform layer, water layer is used chloroform extraction again with the careful acidifying of dilute hydrochloric acid of massfraction 5%, obtains yellow 1-sulfydryl pyrene behind the evaporate to dryness, and yield is 86%.86～89 ℃ of fusing points.
Infrared spectra: KBr, ν (cm
-1): 3038.89 (AR-H), 2920.10 (C – H), 2528.91 (S – H).
Mass spectroscopy: m/z (%): 243 (100, M
+), 202 (95), 117 (20).
Nuclear magnetic data:
1H-NMR (CDCl
3) (400MHz), δ 3.857 (1H, s, S-H), 8.002-8.188 (9H, m, Ar).
Embodiment 3:
1,1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic is synthetic:
Under nitrogen protection, 6.54 gram 1-hydroxyl pyrenes are dissolved in 50 milliliters of N, dinethylformamide, be cooled to 0～5 ℃, slowly add 2.40 gram mass marks and be 60% sodium hydride, stirring reaction 30 minutes, add 6.00 gram dimethylamino sulfo-formyl chlorides, slowly be warming up to 80 ℃; Add 3.25 gram salt of wormwood again, continue reaction 30 hours; Unreacted salt of wormwood is filtered in cooling; Add 100 ml distilled waters, produce yellow mercury oxide, filter, recrystallizing methanol obtains yellow 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic, and yield is 98.0%.
2,1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic is synthetic:
4.0 gram O-1-pyrenyl dimethylamino thiocarboxylics drying, crystal form are joined in the stainless steel cauldron; under the nitrogen protection condition; temperature rises to 260 ℃ of reactions 45 minutes fast; get 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic through column chromatography (methylene dichloride: sherwood oil=2.5:1(volume ratio)), yield is 40.0%.
3,1-sulfydryl pyrene is synthetic: under nitrogen protection, add 1.08 gram potassium hydroxide in the mixing solutions (1:7 volume ratio) of 5 ml waters and 35 milliliters of ethylene glycol, add 2.52 gram S-1-pyrenyl dimethylamino thiocarboxylics again, refluxed 1.5 hours; After the cooling, in reaction soln impouring frozen water, add the chloroform vibration fully, discard chloroform layer, water layer is used chloroform extraction again with the careful acidifying of dilute hydrochloric acid of massfraction 5%, obtains yellow 1-sulfydryl pyrene behind the evaporate to dryness, and yield is 86.5%.
Embodiment 4:
1,1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic is synthetic:
Under nitrogen protection, 6.54 gram 1-hydroxyl pyrenes are dissolved in 50 milliliters of N, dinethylformamide, be cooled to 0～5 ℃, slowly add 2.40 gram mass marks and be 60% sodium hydride, stirring reaction 30 minutes, add 6.00 gram dimethylamino sulfo-formyl chlorides, slowly be warming up to 80 ℃; Add 3.25 gram salt of wormwood again, continue reaction 30 hours; Unreacted salt of wormwood is filtered in cooling; Add 100 ml distilled waters, produce yellow mercury oxide, filter, recrystallizing methanol obtains yellow 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic, and yield is 98%.
2,1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic is synthetic:
4.0 gram O-1-pyrenyl dimethylamino thiocarboxylics drying, crystal form are joined in the stainless steel cauldron; under the nitrogen protection condition; temperature rises to 290 ℃ fast; reacted 45 minutes; get 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic through column chromatography (methylene dichloride: sherwood oil=2.5:1(volume ratio)), yield is 60.5%.
3,1-sulfydryl pyrene is synthetic: under nitrogen protection, add 1.08 gram potassium hydroxide in the mixing solutions (1:7 volume ratio) of 5 ml waters and 35 milliliters of ethylene glycol, add 2.52 gram S-1-pyrenyl dimethylamino thiocarboxylics again, refluxed 1.5 hours; After the cooling, in reaction soln impouring frozen water, add the chloroform vibration fully, discard chloroform layer, water layer is used chloroform extraction again with the careful acidifying of dilute hydrochloric acid of massfraction 5%, obtains yellow 1-sulfydryl pyrene behind the evaporate to dryness, and yield is 86.5%.
Embodiment 5:
1,1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic is synthetic:
Under nitrogen protection, 6.54 gram 1-hydroxyl pyrenes are dissolved in 50 milliliters of N, dinethylformamide, be cooled to 0～5 ℃, slowly add 2.40 gram mass marks and be 60% sodium hydride, stirring reaction 30 minutes, add 6.00 gram dimethylamino sulfo-formyl chlorides, slowly be warming up to 80 ℃; Add 3.25 gram salt of wormwood again, continue reaction 30 hours; Unreacted salt of wormwood is filtered in cooling; Add 100 ml distilled waters, produce yellow mercury oxide, filter, recrystallizing methanol obtains yellow 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic, and yield is 98.0%.
2,1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic is synthetic:
4.0 gram O-1-pyrenyl dimethylamino thiocarboxylics drying, crystal form are joined in the stainless steel cauldron; under the nitrogen protection condition; temperature rises to 285 ℃ fast; reacted 100 minutes; get 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic through column chromatography (methylene dichloride: sherwood oil=2.5:1(volume ratio)); 131～134 ℃ of fusing points, yield are 75.0%.
3,1-sulfydryl pyrene is synthetic: under nitrogen protection, add 1.08 gram potassium hydroxide in the mixing solutions (1:7 volume ratio) of 5 ml waters and 35 milliliters of ethylene glycol, add 2.52 gram S-1-pyrenyl dimethylamino thiocarboxylics again, refluxed 1.5 hours; After the cooling, in reaction soln impouring frozen water, add the chloroform vibration fully, discard chloroform layer, water layer is used chloroform extraction again with the careful acidifying of dilute hydrochloric acid of massfraction 5%, obtains yellow 1-sulfydryl pyrene behind the evaporate to dryness, and yield is 86.5%.
Embodiment 6:
1,1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic is synthetic:
Under nitrogen protection, 6.54 gram 1-hydroxyl pyrenes are dissolved in 50 milliliters of N, dinethylformamide, be cooled to 0～5 ℃, slowly add 2.40 gram mass marks and be 60% sodium hydride, stirring reaction 30 minutes, add 6.00 gram dimethylamino sulfo-formyl chlorides, slowly be warming up to 80 ℃; Add 3.25 gram salt of wormwood again, continue reaction 30 hours; Unreacted salt of wormwood is filtered in cooling; Add 100 ml distilled waters, produce yellow mercury oxide, filter, recrystallizing methanol obtains yellow 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic, and yield is 98.0%.
2,1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic is synthetic:
4.0 gram O-1-pyrenyl dimethylamino thiocarboxylics drying, crystal form and 4.0 gram phenyl ether mixtures are joined in the stainless steel cauldron; under the nitrogen protection condition; temperature rises to 290 ℃ fast; react after 70 minutes; cooling gets 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic by column chromatography (methylene dichloride: sherwood oil=2.5:1(volume ratio)), and yield is 87.2%.
3,1-sulfydryl pyrene is synthetic: under nitrogen protection, add 1.08 gram potassium hydroxide in the mixing solutions (1:7 volume ratio) of 5 ml waters and 35 milliliters of ethylene glycol, add 2.52 gram S-1-pyrenyl dimethylamino thiocarboxylics again, refluxed 1.5 hours; After the cooling, in reaction soln impouring frozen water, add the chloroform vibration fully, discard chloroform layer, water layer is used chloroform extraction again with the careful acidifying of dilute hydrochloric acid of massfraction 5%, obtains yellow 1-sulfydryl pyrene behind the evaporate to dryness, and yield is 86.5%.
Claims (1)
1. method for preparing 1-sulfydryl pyrene and midbody compound thereof, it is characterized in that: at first synthetic 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic, utilize rearrangement reaction then, generate 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic, hydrolysis forms 1-sulfydryl pyrene again;
The reaction formula of 1-sulfydryl pyrene and 1-sulfydryl pyrene midbody compound is expressed as follows:
Concrete grammar is as follows:
Synthesizing of described 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic:
Under nitrogen protection, 1-hydroxyl pyrene is dissolved in N, and dinethylformamide (DMF) is cooled to 0～5 ℃, slowly adds massfraction and be 60% sodium hydride, stirring reaction 30 minutes; Add dimethylamino sulfo-formyl chloride (DMTCC), be warming up to 80 ℃; Add an amount of salt of wormwood again, continue reaction 30 hours, unreacted salt of wormwood is filtered in cooling; Add big water gaging, produce yellow mercury oxide, filter, recrystallizing methanol gets yellow 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic, and yield is 98.0%;
Molecular structure and the crystalline structure of 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic:
These compound crystal data, crystallographic system: monocline; Spacer: P2
1Molecular formula: C
19H
15ONS; Molecular weight: 305.38; Unit cell parameters: a=10.3571 (6)
B=18.9930 (11)
C=15.3449 (9)
α=90.00 °, β=90.702 (4) °, γ=90.00 °; Unit cell volume: 3018.3 (3)
Temperature: 296 (2) K; Structure cell density: 1.344g cm
– 3Structure factor (F (000)): 1280; Absorption factor: 0.215mm
– 1Can observe S value (the GOF on F of point diffraction
2): 1.021; The factor [I〉2sigma (I)]: R as a result
1=0.0774, wR
2=0.1020.137～139 ℃ of fusing points;
Synthesizing of described 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic:
The O-1-pyrenyl dimethylamino thiocarboxylic of drying crystalline attitude is joined in the stainless steel cauldron, exist or the disappearance solvent, under the nitrogen protection condition, temperature rises to 260～290 ℃ fast, reacted 45～100 minutes, get 1-sulfydryl pyrene intermediate S-1-pyrenyl dimethylamino thiocarboxylic through column chromatography for separation, yield is 40.0～87.2%;
Molecular structure and the crystalline structure of 1-sulfydryl pyrene intermediate O-1-pyrenyl dimethylamino thiocarboxylic:
These compound crystal data, crystallographic system: quadrature; Spacer: Pbca; Molecular formula: C
19H
15ONS; Molecular weight: 305.38; Unit cell parameters: unit cell parameters: a=13.08 (2)
B=19.45 (3)
C=23.40 (4)
α=90.00 °, β=90.00 °, γ=90.00 °; Unit cell volume: 5953 (18)
Temperature: 123 (2) K; Structure cell density: 1.363g cm
– 3Structure factor (F (000)): 2560; Absorption factor: 0.218mm
– 1Can observe S value (the GOF on F of point diffraction
2): 0.957; The factor [I〉2sigma (I)]: R as a result
1=0.0690, wR
2=0.1077.131～134 ℃ of fusing points;
Synthesizing of described 1-sulfydryl pyrene:
Under nitrogen protection, in the mixing solutions of water and ethylene glycol, add potassium hydroxide, the 1:7 volume ratio adds S-1-pyrenyl dimethylamino thiocarboxylic again, refluxes 1.5 hours; After the cooling, in reaction soln impouring frozen water, add the chloroform vibration fully, discard chloroform layer, water layer is used chloroform extraction again with the careful acidifying of dilute hydrochloric acid of massfraction 5%, obtains yellow 1-sulfydryl pyrene behind the evaporate to dryness, and yield is 86.5%;
1-sulfydryl pyrene contains pyrenyl luminophore and mercapto functional group, and molecular structure is as follows:
86～89 ℃ of fusing points.
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| CN104003906A (en) * | 2014-06-11 | 2014-08-27 | 内蒙古民族大学 | Pyrene fluorescence probe and preparation method and application thereof |
| CN105061308A (en) * | 2015-08-04 | 2015-11-18 | 济南大学 | Preparation method and application of high selectivity ultrasensitive inorganic mercury / organic mercury ion fluorescent probe |
| CN109096160A (en) * | 2018-09-10 | 2018-12-28 | 浙江扬帆新材料股份有限公司 | A method of it is prepared using continuous flow reactor and replaces benzenethiol and heterocycle thiophenol |
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| US20100113722A1 (en) * | 2007-09-20 | 2010-05-06 | Ben-Gurion University Of The Negev Research And Development Authority | Sulfur chelated ruthenium compounds useful as olefin metathesis catalysts |
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| SU518497A1 (en) * | 1974-08-26 | 1976-06-25 | Предприятие П/Я В-8611 | The method of obtaining pyreno / 3,4-s / thiopyranone-3 (2n) |
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| US20100113722A1 (en) * | 2007-09-20 | 2010-05-06 | Ben-Gurion University Of The Negev Research And Development Authority | Sulfur chelated ruthenium compounds useful as olefin metathesis catalysts |
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| KEN MATSUMOTO ET AL.: "Cannabinoids. 1. 1-Amino- and l-Mercapto-7,8,9,1O-tetrahydro-6H-dibenzo[b,d]pyrans", 《JOURNAL OF MEDICINAL CHEMISTRY》, vol. 20, no. 1, 31 December 1977 (1977-12-31), pages 17 - 24 * |
| YING CHEN ET AL.: "Antitumor agents 292. Design, synthesis and pharmacological study of S- and O-substituted 7-mercapto- or hydroxy-coumarins and chromones as potent cytotoxic agents", 《EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY》, vol. 49, 29 December 2011 (2011-12-29), pages 74 - 85, XP028896357, DOI: doi:10.1016/j.ejmech.2011.12.025 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003906A (en) * | 2014-06-11 | 2014-08-27 | 内蒙古民族大学 | Pyrene fluorescence probe and preparation method and application thereof |
| CN104003906B (en) * | 2014-06-11 | 2015-06-24 | 内蒙古民族大学 | Pyrene fluorescence probe and preparation method and application thereof |
| CN105061308A (en) * | 2015-08-04 | 2015-11-18 | 济南大学 | Preparation method and application of high selectivity ultrasensitive inorganic mercury / organic mercury ion fluorescent probe |
| CN105061308B (en) * | 2015-08-04 | 2017-10-13 | 济南大学 | The preparation method and application of inorganic mercury/organic mercury ion fluorescence probe |
| CN109096160A (en) * | 2018-09-10 | 2018-12-28 | 浙江扬帆新材料股份有限公司 | A method of it is prepared using continuous flow reactor and replaces benzenethiol and heterocycle thiophenol |
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