CN104447452A - Synthetic method of mercapto functionalized polyaryl carboxylic acid compound - Google Patents
Synthetic method of mercapto functionalized polyaryl carboxylic acid compound Download PDFInfo
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Abstract
The invention relates to the technical field of compound synthesis and in particular discloses a synthetic method of a mercapto functionalized polyaryl carboxylic acid compound. The synthetic method concretely comprises the following steps: in the presence of a palladium catalyst, putting aryl fluoride, aryl boric acid and alkali metal salt serving as raw materials into a mixed system of water/organic solvent, and carrying out a series of subsequent reactions including Suzuki reaction to obtain the mercapto functionalized polyaryl carboxylic acid compound. According to the synthetic method disclosed by the invention, as the Suzuki reaction is realized in the air environment firstly, the reaction condition is greatly simplified, the reaction time is shortened from 2d to 1h, and the productivity and the yield are greatly increased; in addition, by adopting the environment-friendly solvent, the environment is beneficially protected; the mercapto functionalized polyaryl carboxylic acid compound synthesized by utilizing the synthetic method can be largely applied to metal organic compounds to build a series of novel porous materials with novel structures and excellent performances.
Description
Technical field
The present invention relates to a kind of new synthetic method of thiohydroxy-containing group's compound, be specifically related to the new synthetic method of mercapto-functionalized aryl carboxylic acid compound.
Background technology
Sulfhydryl compound comprises mercaptan and the large class of thiophenol two, important industrial chemicals and medicine intermediate, sulphur contained by sulfhydryl compound relates to the hybridized orbital of larger 3s/3p composition and the less 1s track Cheng Jian of hydrogen, so S-H key is more weak, makes the compound of thiohydroxy-containing group have slightly acidic.The sulfydryl of sulfhydryl compound easily and the quick complexing of the heavy metal ion such as mercury ion, silver ions, and forms stable coordination compound.Therefore, the compound of thiohydroxy-containing group, can be used for the removing toxic substances (Manuel Algarra a, Mar í a Isabel V á zquez. Chem. Eng. J. 2014,253,472 – 477) of heavy metal ion on the one hand; On the other hand, can be used for the application upper (Jun He, Meiqin Zha, Zhengtao Xu. J. Am. Chem. Soc. 2013,135,7,807 7810) such as the separation and consentration of heavy metal ion, quantitative and qualitative analysis.
In recent years, metal-organic framework materials (Metal-Organic framework, MOF) be rapidly developed as emerging porous material, the advantage of this polyporous materials is to carry out cutting by the design of organic functional molecular to the function of porous material.Therefore, its difficulty is design and synthesis organic functional molecular.Work based on a large amount of early stage finds, sulfydryl aromatic carboxylic acids, has annexed soft or hard atom and be integrated (hsab theory).S wherein on sulfydryl is as soft base, and the O on carboxyl is as hard base, this compounds formed metal-organic framework materials time, obvious advantage in having.When selection hard acid metalloid ion is as (Zr
4+) as centered by joining, central ion can be selected to form metal organic frame with carboxyl, and sulfydryl does not participate in coordination, dissociate and modify framework material (Ka-Kit Yee, Zhengtao Xu.J. Am. Chem. Soc.2013,135,7795-7798).Sulfydryl is incorporated in metal-organic framework materials, and its advantage major embodiment is as follows: 1) the strong keying action of mercapto functional group and metal ion makes MOF material can absorb various different metal ion thus reaches the object of heavy-metal ion removal; 2) mercapto functional group the activity in organic be conducive to MOF material carry out after synthetic modification, such as inside the duct of MOF material, carry out cross-coupling reaction thus research high molecular polymer and the synergistic effect of solid-state framework material.
In addition S-H key is active; synthesis easily carries out cutting and modification to it; sulfydryl is converted into thioether; make it functional stronger; more strong (Jun He, Ka-Kit Yee, the Zhengtao Xu. Chem. Mater. 2011 of the such as adsorption of heavy metal ion; 23,2940 – 2947; Xiao-Ping Zhou, Zhengtao Xu. Chem. Commun., 2009,5439 – 5441.).Based on the importance of this compounds, it is very important for inventing a kind of novel method that is efficient, low cost synthesis sulfhydrylation aryl compound.
Consider the activity of sulfydryl, general sulfydryl synthetic method, major part is all synthesize sulfhydryl compound by comparatively exacting terms, loaded down with trivial details step and lower productive rate, what is more important we find, that has reported up to now only has an example containing mercapto-functionalized aromatic carboxylic acid.The people such as Laurent Vial. for raw material with 2,5-Dihydroxyterephthalic acid ethyl ester, introduce dimethylamino sulfo-formyl chloride small molecules, by reactions steps such as rearrangement, hydrolysis, obtain 2,5-dimercapto terephthalic acids (see formula 1).
Utilize method described in formula 1 to synthesize mercapto-functionalized aryl carboxylic acid compounds, each step needs strict oxygen free condition, complex operation, and reaction time is long, and productive rate is lower.And method is comparatively large by raw-material restriction, especially when more how mercapto-functionalized aromatic carboxylic acids explored by current needs, its universality is obviously inadequate.
Summary of the invention
Technical problem to be solved by this invention overcomes in prior art the above-mentioned defect of synthesizing existing for mercapto-functionalized aryl carboxylic acid compounds, provides that a kind of new high efficiency, mild condition, reaction efficiency are high, cost is low, is easy to the synthetic method of the sulfhydrylation polyaryl carboxylic acids compound that large-scale industrialization is produced.
Second object of the present invention is to provide the sulfhydrylation polyaryl carboxylic acids compound obtained by aforesaid method.
The object of the invention is to be achieved by the following technical programs:
A synthetic method for mercapto-functionalized polyaryl carboxylic acids compound, comprises the following steps:
S1. under palladium catalyst, starting aryl fluorochemical, aryl boric acid and an alkali metal salt are placed in water/organic solvent mixed system, synthesize to obtain intermediate 1 by suzuki reaction;
S2. by intermediate 1, sodium methyl mercaptide and chloride compounds in an inert atmosphere Reactive Synthesis obtain intermediate 2;
S3. intermediate 2 Reactive Synthesis that is hydrolyzed under strongly alkaline conditions obtains end product.
The first step of the present invention obtains intermediate 1 by suzuki reaction, it will be apparent to those skilled in the art that suzuki reaction be palladium under catalysis, aryl or ene boric acid or boric acid ester and chlorine, bromine, iodo aromatic hydrocarbon or alkene generation cross-coupling reaction.The catalyzer of general Suzuki linked reaction is all anaerobism, so when reacting, deoxygenation is an indispensable step.
Present invention applicant is at exploration synthesis 2 ', 5 '-dimercapto-p-terphenyl-4 ', during 4 '-dioctyl phthalate, synthetic method (see formula 2) first traditionally.
From above-mentioned reaction formula, go to synthesize mercapto-functionalized polyaryl carboxylic acids compound by traditional method, embody the deficiencies such as length reaction time, severe reaction conditions.These shortcomings constitute huge obstacle to large-scale industrial production, and simultaneously harsh reaction conditions and the themes of the times of low-carbon environment-friendly are contrary.
In order to adapt to the call of Sustainable development, substitute with environmentally friendly reaction medium the important research target that traditional poisonous, volatile organic solvent are contemporary Green Chemistry, have the water/organic solvent reaction systems such as water-PEG, water-ethanol, boiling at present and be applied to Suzuki linked reaction.But suzuki reaction has selectivity, the activity that the same halogen of different halogen and different positions carries out reacting has difference, the consumptions of its material etc. all can affect the productive rate of finalization compound, the present invention for the character of the hydroxy functionalized polyaryl carboxylic acids compound that will obtain, obtains synthetic method of the present invention on the basis of suzuki reaction.
Preferably, the organic solvent in described mixed system be selected from DMI, DMF, N,N-dimethylacetamide, N, N-diethylformamide, ethanol, poly(oxyethylene glycol) 400 and Polyethylene Glycol-600 one or more.
Preferably, described an alkali metal salt be selected from potassium acetate, potassiumphosphate, sodium carbonate, salt of wormwood and cesium carbonate one or more.
Preferably, described palladium catalyst be selected from tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, Palladous chloride and acid chloride one or both.
Preferably, described chloride compounds be selected from Acetyl Chloride 98Min., trichoroacetic chloride, valeryl chloride, butyryl chloride one or more.
Preferably, the mol ratio of described aryl fluorides, aryl boric acid, an alkali metal salt and palladium catalyst is 1:2 ~ 3:4 ~ 6:0.01 ~ 0.02.
Preferably, described aryl fluorides is selected from fluoro-2, the 5-dibromobenzenes of Isosorbide-5-Nitrae-two, and aryl boric acid is selected from 4-cyanophenylboronic acid.
Further, when being raw material with fluoro-2, the 5-dibromobenzenes of Isosorbide-5-Nitrae-two and 4-cyanophenylboronic acid, the synthetic method of above-mentioned mercapto-functionalized polyaryl carboxylic acids compound comprises the following steps:
S1. under palladium catalyst, fluoro-for raw material Isosorbide-5-Nitrae-two 2,5-dibromobenzenes, 4-cyanophenylboronic acid and an alkali metal salt are placed in water/organic solvent mixed system, within 0.5 ~ 12 hour, synthesize to obtain intermediate 1 by reaction at suzuki reaction 25 ~ 100 DEG C;
S2. intermediate 2 within 12 ~ 24 hours, is synthesized to obtain by reacting at intermediate 1, sodium methyl mercaptide and chloride compounds in an inert atmosphere 25 ~ 300 DEG C;
S3. intermediate 2 obtains end product in the strong alkaline condition reaction synthesis in 0.5 ~ 12 hour at 25 ~ 150 DEG C that is hydrolyzed.
The reaction formula of above-mentioned building-up process is as follows:
Described Solvent represents water/organic mixed solvent; RT represents room temperature; Air represents air ambient; [Pd] represents the compound of palladium catalyst; Base is an alkali metal salt; X=1,2,3 ... n.
Fluoro-2, the 5-dibromobenzenes of described Isosorbide-5-Nitrae-two: 4-cyanophenylboronic acid: an alkali metal salt: the mol ratio of catalyzer is 1:2 ~ 3:4 ~ 6:0.01 ~ 0.02.
Described raw material: sodium methyl mercaptide: the mol ratio of chloride compounds is 1:10 ~ 20:15 ~ 30.
When selected organic solvent is ethanol, the volume ratio of ethanol and water is 0.5 ~ 2:1; When the organic solvent selected is N,N-dimethylacetamide, volume ratio 0.5 ~ 3.5:1.
Described strong alkaline condition, is selected from the aqueous ethanolic solution of sodium hydroxide or potassium hydroxide.
Compared with prior art, the invention has the beneficial effects as follows:
The invention provides a kind of synthetic method of mercapto-functionalized polyaryl carboxylic acids compound; specifically starting aryl fluorochemical, aryl boric acid and an alkali metal salt are placed in water/organic solvent mixed system under palladium catalyst to be obtained by follow-up series reaction such as suzuki reactions; traditional suzuki reaction all needs just can carry out under protection of inert gas and palladium complex catalyst condition, embodies the deficiencies such as length reaction time, severe reaction conditions, productive rate be low.These shortcomings constitute huge obstacle to large-scale industrial production; and the present invention achieves reaction under air ambient; greatly simplifie reaction conditions; reaction times has shortened to 1 h from 2 d; greatly increase productive rate and output; and adopt environmentally friendly solvent, be beneficial to protection of the environment.
Synthetic method of the present invention is compared to traditional method, and present method simplifies synthesis step, decreases the use to solvent, significantly improves production efficiency, environmental protection and energy saving, be beneficial to industrialization promotion.This synthetic method improves its universality.Synthesized can be widely used in the metal-organic novel porous materials constructing a series of novel structure of formation, excellent performance containing mercapto-functionalized aryl carboxylic acid compound.
Accompanying drawing explanation
The fluoro-p-terphenyl-4,4 ' of Fig. 1 intermediate 2 ', 5 ' ,-two ' the nucleus magnetic hydrogen spectrum figure of-dintrile;
The fluoro-p-terphenyl-4,4 ' of Fig. 2 intermediate 2 ', 5 ' ,-two ' the nuclear-magnetism fluorine spectrogram of-dintrile;
The fluoro-p-terphenyl-4,4 ' of Fig. 3 intermediate 2 ', 5 ' ,-two ' infrared spectrum of-dintrile;
Fig. 4 intermediate 2 ', 5 ' ,-two valeryl thiol group-p-terphenyl-4,4 ' ' the nucleus magnetic hydrogen spectrum figure of-dintrile;
Fig. 5 intermediate 2 ', 5 ' ,-two valeryl thiol group-p-terphenyl-4,4 ' ' infrared spectrum of-dintrile;
Fig. 6 target product 2 ', 5 ' ,-dimercapto-p-terphenyl-4,4 ' ' the nucleus magnetic hydrogen spectrum figure of-dioctyl phthalate;
Fig. 7 target product 2 ', 5 ' ,-dimercapto-p-terphenyl-4,4 ' ' infrared spectrum of-dioctyl phthalate.
Embodiment
Further illustrate content of the present invention below in conjunction with the drawings and specific embodiments, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the simple modification do the inventive method, step or condition or replacement, all belong to scope of the present invention.If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art.
embodiment 12 ', 5 '-dimercapto-p-terphenyl-4 ', the synthesis qualification of 4 '-dioctyl phthalate
(1) 2 ', 5 '-two fluoro-p-terphenyl-4 ', the synthesis qualification of 4 '-dintrile
First be traditional method (method 1); by fluoro-for Isosorbide-5-Nitrae-two 2,5-dibromobenzene (1089mg; 4 mmol), 4-cyanophenylboronic acid (1293 mg; 8.8 mmol), the single port flask of palladium compound 50 mL of salt of wormwood (2210 mg, 16 mmol) and catalytic amount, under nitrogen protection; add the toluene aqueous solution of 40 mL deoxygenation; reflux at 90 DEG C 2 d, through silica gel column chromatography separating-purifying, obtains white powder product (intermediate
1) 443 mg, yield 35%, i.e. intermediate 1.
The present embodiment uses following method (method 2) synthetic intermediate 1
Novel method of the present invention, by fluoro-for Isosorbide-5-Nitrae-two 2,5-dibromobenzenes (1088 mg, 4 mmol), 4-cyanophenylboronic acid (1292 mg, 8.8 mmol), the palladium compound of salt of wormwood (2208 mg, 16 mmol) and catalytic amount is placed in the single port flask of 50 mL, adds aqueous ethanolic solution (volume ratio of ethanol and water is 1:1), stirring at normal temperature 1 h under air ambient, through silica gel column chromatography separating-purifying, obtain white powder product 544 mg, yield 43%.Spectrum Analysis confirms gained intermediate
1be intermediate 2 ', 5 ' ,-two fluoro-p-terphenyl-4,4 ' '-dintrile, spectral data is as follows:
1h NMR (400 MHz, DMSO) δ
h: 8.02 (d,
j=8.5 Hz, 1H), 7.87 (d,
j=8.3 Hz, 1H), 7.75 (t,
j=8.9 Hz, 1H);
19f NMR (377 MHz, DMSO) δ
f:-122.26 (s, 1H). IR (ν/cm
-1): 3044 (w), 2226 (s), 1606 (m), 1483 (s), 1394 (s), 1269 (m), 1170 (s), 842 (s), 553 (s)
(2) 2 ', 5 '-two valeryl thiol group-p-terphenyl-4 ', the synthesis qualification of 4 '-dintrile
In 4 mL 1,2-in-1 intermediate 1 (480 mg becoming to obtain of aforesaid method are added in 3-dimethyl-2-imidazolinone, 1.5 mmol) and sodium methyl mercaptide (1500 mg, 21.4 mmol) reflux 24 h afterwards, react complete and be cooled to room temperature, then add valeryl chloride (1.8 mL, 15.2 mmol), stir 12 h.Add 50 mL distilled water diluting reaction solutions, separate out solid, through silica gel column chromatography separating-purifying, obtain Tan solid product 400 mg, yield 52%.Spectrum Analysis confirms gained intermediate
2be intermediate 2 ', 5 ' ,-two valeryl thiol group-p-terphenyl-4,4 ' '-dintrile, spectral data is as follows:
1h NMR (400 MHz, CDCl
3) δ
h: 7.73 (d,
j=8.4 Hz, 1H), 7.58 (s, 1H), 7.52 (d,
j=8.4 Hz, 1H), 2.51 (t,
j=7.4 Hz, 1H), 1.57 – 1.46 (m, 1H), 1.22 (dq,
j=14.6,7.3 Hz, 1H), 0.87 (t,
j=7.3 Hz, 1H). IR (ν/cm
-1): 3068 (w), 3036 (w), 2956 (m), 2926 (m), 2225 (s), 1704 (s), 1606 (m), 1467 (s), 1139 (m), 1032 (s), 840 (m), 566 (m).
(3) the synthesis qualification of end product
Intermediate is added in the aqueous ethanolic solution of 15 mL potassium hydroxide
2(400 mg, 0.78 mmol), reflux 5 h, reacts complete and be cooled to room temperature, adds excessive concentrated hydrochloric acid, decompress filter, obtains light brown solid product (intermediate
3) 270 mg, yield 91%.Spectrum Analysis confirms gained compound
3be end product 2 ', 5 ' ,-dimercapto-p-terphenyl-4,4 ' '-dioctyl phthalate, spectral data is as follows:
1h NMR (400 MHz, DMSO) δ
h: 7.70 (d,
j=8.1 Hz, 1H), 7.49 (s, 1H), 7.03 (d,
j=8.0 Hz, 1H). IR (ν/cm
-1): 2666 (w), 2545 (w), 1691 (s), 1606 (s), 1419 (s), 1286 (s), 1014 (m), 855 (m), 709 (m).
comparative example 1
In building-up process for end product described in embodiment 1, the factor A that setting affects Yield of final product is the volume ratio of water and ethanol in water/organic solvent system; Factor B is the mol ratio of fluoro-2, the 5-dibromobenzenes of Isosorbide-5-Nitrae-two, 4-cyanophenylboronic acid, an alkali metal salt and palladium catalyst; Factor C is intermediate 1: sodium methyl mercaptide: the mol ratio of chloride compounds; Factor D is the temperature of suzuki reaction; Factor E is the time of suzuki reaction.
Above-mentioned each factor sets 3 levels, investigate the impact of each factor on the end product intermediate 1 of preparation method's acquisition or the productive rate of end product described in embodiment 1 ~ 3, wherein factor C is the impact on Yield of final product, and other factors are the impacts on intermediate 1 productive rate, and result is as table 1.
embodiment 22 ', 5 '-dimercapto-p-terphenyl-4 ', the synthesis qualification of 4 '-dioctyl phthalate
Synthetic method is with embodiment 1, and unique unlike when synthetic intermediate 1, the organic solvent in water used/organic solvent mixed system is poly(oxyethylene glycol) 400, and the volume ratio of definition water and poly(oxyethylene glycol) 400 is factor E.
embodiment 32 ', 5 '-dimercapto-p-terphenyl-4 ', the synthesis qualification of 4 '-dioctyl phthalate
Synthetic method is with embodiment 1, and unique unlike when synthetic intermediate 1, the organic solvent in water used/organic solvent mixed system is Polyethylene Glycol-600, and the volume ratio of definition water and Polyethylene Glycol-600 is factor F.
embodiment 42 ', 5 '-dimercapto-p-terphenyl-4 ', the synthesis qualification of 4 '-dioctyl phthalate
Synthetic method is with embodiment 1, and unique unlike when synthetic intermediate 1, the organic solvent in water used/organic solvent mixed system is N,N-dimethylacetamide, and the volume ratio of definition water and N,N-dimethylacetamide is factor G.
comparative example 2
In investigation embodiment 2 ~ 4, factor E, F, G are on the impact of intermediate 1 productive rate, and result is as table 2.
Claims (9)
1. a preparation method for mercapto-functionalized polyaryl carboxylic acids compound, is characterized in that, comprise the following steps:
S1. under palladium catalyst, starting aryl fluorochemical, aryl boric acid and an alkali metal salt are placed in water/organic solvent mixed system, within 0.5 ~ 12 hour, are prepared into intermediate 1 by reaction at suzuki reaction 25 ~ 100 DEG C;
S2. within 12 ~ 24 hours, intermediate 2 is prepared into by reacting at intermediate 1, sodium methyl mercaptide and chloride compounds in an inert atmosphere 25 ~ 300 DEG C;
S3. intermediate 2 prepares end product in 0.5 ~ 12 hour in the strong alkaline condition reaction at 25 ~ 150 DEG C that is hydrolyzed.
2. preparation method according to claim 1, it is characterized in that, organic solvent in described mixed system is selected from 1,3-dimethyl-2-imidazolinone, N, dinethylformamide, N, one or more in N-N,N-DIMETHYLACETAMIDE, N, N-diethylformamide, ethanol, poly(oxyethylene glycol) 400 and Polyethylene Glycol-600.
3. preparation method according to claim 2, is characterized in that, the organic solvent in described mixed system is selected from ethanol, and the volume ratio of ethanol and water is 0.5 ~ 2:1.
4. preparation method according to claim 1, is characterized in that, the mol ratio of described aryl fluorides, aryl boric acid, an alkali metal salt and palladium catalyst is 1:2 ~ 3:4 ~ 6:0.01 ~ 0.02.
5. preparation method according to claim 1, is characterized in that, described an alkali metal salt be selected from potassium acetate, potassiumphosphate, sodium carbonate, salt of wormwood and cesium carbonate one or more.
6. preparation method according to claim 1, is characterized in that, described palladium catalyst be selected from tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, Palladous chloride and acid chloride one or both.
7. the preparation method according to claim 1 or 4, is characterized in that, described aryl fluorides is selected from fluoro-2, the 5-dibromobenzenes of Isosorbide-5-Nitrae-two, and aryl boric acid is selected from 4-cyanophenylboronic acid.
8. preparation method according to claim 1, is characterized in that, described chloride compounds be selected from Acetyl Chloride 98Min., trichoroacetic chloride, valeryl chloride, butyryl chloride one or more.
9. preparation method according to claim 7, is characterized in that, described intermediate 1: sodium methyl mercaptide: the mol ratio of chloride compounds is 1:10 ~ 20:15 ~ 30.
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Cited By (3)
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| CN106496080A (en) * | 2016-10-19 | 2017-03-15 | 广东工业大学 | A kind of preparation method of mercapto-functionalized aryl carboxylic acid |
| CN107337626A (en) * | 2017-08-04 | 2017-11-10 | 广东工业大学 | A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof |
| CN107383079A (en) * | 2017-08-04 | 2017-11-24 | 广东工业大学 | A kind of metal-organic framework materials and its synthetic method based on alkyl hydrosulfide modification |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496080A (en) * | 2016-10-19 | 2017-03-15 | 广东工业大学 | A kind of preparation method of mercapto-functionalized aryl carboxylic acid |
| CN106496080B (en) * | 2016-10-19 | 2019-01-15 | 广东工业大学 | A kind of preparation method of mercapto-functionalized aryl carboxylic acid |
| CN107337626A (en) * | 2017-08-04 | 2017-11-10 | 广东工业大学 | A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof |
| CN107383079A (en) * | 2017-08-04 | 2017-11-24 | 广东工业大学 | A kind of metal-organic framework materials and its synthetic method based on alkyl hydrosulfide modification |
| CN107383079B (en) * | 2017-08-04 | 2020-06-09 | 广东工业大学 | Metal organic framework material based on alkyl mercaptan modification and synthetic method thereof |
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