CN108499606B - O-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst and preparation method and application thereof - Google Patents

O-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst and preparation method and application thereof Download PDF

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CN108499606B
CN108499606B CN201710102050.4A CN201710102050A CN108499606B CN 108499606 B CN108499606 B CN 108499606B CN 201710102050 A CN201710102050 A CN 201710102050A CN 108499606 B CN108499606 B CN 108499606B
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王暖程
尚永华
王玉启
李海军
石滨
朱智诚
华卫琦
黎源
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
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    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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Abstract

The invention relates to an o-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst, a preparation method and application thereof. The catalyst is prepared from the following components: (A) ortho-mercaptoarylimidazolium salts and (B) transition metal salts. The catalyst can be used for catalyzing the self-polymerization of diisocyanate to prepare a polyisocyanate curing agent, and is particularly suitable for catalyzing the self-polymerization of toluene diisocyanate to prepare toluene diisocyanate trimer. Solves the problem of high polymer, and can obtain products with excellent molecular weight distribution, and the free monomer in the products is controlled below 0.3 wt%.

Description

O-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to an o-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst, a preparation method and application thereof.
Background
There have been a number of reports in the literature on the preparation of isocyanurate-containing polyisocyanate compounds for a long time. Aliphatic and aromatic isocyanate trimerics are widely used in the field of primer materials or polyurethane elastomers and polyurethane foams.
Isocyanate monomers are not generally used directly in the coatings industry due to their high volatility and toxicity. From the point of view of occupational health and hygiene, the conversion thereof into trimers having a low free monomer content is one of the main application forms at present. At present, the reduction of free monomers is mainly realized by two ways of film evaporation or direct synthesis method for improving the conversion rate, and the latter method is mainly applied to the preparation process of TDI tripolymer.
Compared with thin film evaporation, the direct synthesis method undoubtedly greatly reduces energy consumption, and simultaneously can solve a series of problems generated in the recycling process of the monomers. However, simply increasing the conversion by continuous trimerization to reduce the monomer content increases the polymer content in the product, which leads to an increase in viscosity and a lower NCO value, and also leads to a deterioration in the compatibility of the curing agent with the resin.
Catalyst molecular design is the focus of much attention in another patent, and proper molecular design can achieve high catalytic effect. GB949253 describes a basic metal carboxylate catalyst which is capable of preparing TDI trimer under the co-catalysis of N-substituted carbamate at 50-70 ℃, wherein the NCO value of the obtained product is 13-15%, the monomer content is lower than 1.25%, the low free standard is not reached, the solubility of the metal carboxylate is poor, a phase transfer catalyst or a surfactant needs to be added into the system, and the catalytic system is undoubtedly more complex and even the downstream application is influenced. In addition to the fact that the phosphine compound is selected as a TDI trimerization catalyst in DE1201992, a product with qualified monomers is not obtained yet, the phosphine catalyst, particularly the aliphatic substituted phosphine compound, is sensitive to air and easy to ignite, and moreover, the phosphine substance belongs to a highly toxic substance, so that the safety risk in the production process is undoubtedly greatly increased. Moreover, the phosphine is used as a catalyst, and a large amount of uretdione is inevitably generated in the reaction process. US4115373 describes a high efficiency catalyst of Mannich base type, which can give a product with acceptable free monomer quality, but which has high activity and uncontrollable molecular weight distribution. Although the design of the novel catalyst solves the problem of free monomer content, the defect of high polymer content of the product obtained by the direct synthesis process cannot be avoided. Therefore, how to solve the problem that the product obtained by the direct synthesis method has a high polymer content, so that the product can obtain a molecular weight distribution close to that of high vacuum film evaporation, and meanwhile, the problem that the free monomer in the product meets the standard is a problem to be solved urgently, and is a new challenge in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides an o-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst and a preparation method thereof.
The invention also aims to provide the application of the o-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst as the catalyst in the preparation of the polyisocyanate curing agent with controllable molecular weight distribution through the self-polymerization reaction of diisocyanate, which not only solves the problem of higher polymer in the direct chemical synthesis method of the curing agent, but also can obtain products with excellent molecular weight distribution, and the free monomer in the products is controlled to be below 0.3 wt%.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
an o-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst comprises the following components: (A) ortho-mercaptoarylimidazolium salts and (B) transition metal salts.
The mass ratio of the catalyst raw material components (A) to (B) is (20-55): (45-80).
The o-mercapto aryl imidazole salt (A) is selected from one or more compounds in structural formulas I, II, III and IV,
Figure BDA0001232018210000031
wherein R is1Is hydrogen, halogen, alkyl or alkoxy, preferably halogen or C1-C10 alkyl, more preferably C1-C10 alkyl;
R2is halogen, alkyl, alkoxy or acetamido, preferably halogen or C1-C10 alkyl, more preferably C1-C10 alkyl;
R3is alkyl, cycloalkyl or benzyl, preferably benzyl.
Specifically, examples of the (A) o-mercaptoarylimidazolium salt include, but are not limited to, N- (2-mercapto-5-tert-butylphenyl) -N '- (2', 4 ', 6' -trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-5-acetylaminophenyl) -N '- (2', 4 ', 6' -trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-5-methoxyphenyl) -N '- (2', 4 ', 6' -trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-5-bromophenyl) -N '- (2', 4, N- (2-mercapto-3, 5-dimethylphenyl) -N '- (2', 4 ', 6' -trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-3, 5-difluorophenyl) -N '- (2', 4 ', 6' -trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-3, 5-dichlorophenyl) -N '- (2', 4 ', 6' -trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-3, 5-dimethylphenyl) -N '-benzyl-imidazolium bromide, N- (2-mercapto-3, 5-dimethylphenyl) -N' -butyl-imidazolium bromide, N- (2-mercapto-3, 5, N- (2-mercapto-3, 5-dimethylphenyl) -N '-isobutyl-imidazole bromide salt, N- (2-mercapto-3, 5-dimethylphenyl) -N' -propyl-imidazole bromide salt, N-beta- (. alpha. -mercaptonaphthyl) -N '- (2', 4 ', 6' -trimethylphenyl) -imidazole bromide salt, n- [4- (2-methyl-3-mercapto) furyl ] -N '- (2', 4 ', 6' -trimethylphenyl) -imidazole bromide salt, N- [3- (2-mercapto) thienyl ] -N '- (2', 4 ', 6' -trimethylphenyl) -imidazole bromide salt.
The invention also provides a preparation method of the (A) o-mercaptoarylimidazolium salt, which comprises the following steps:
(1) dissolving a corresponding sulfhydryl substituted aromatic compound and alkali in alcohol, dropwise adding an iodine alcohol solution into the system at room temperature, continuing to react for 1-3h after dropwise adding, adding a sodium sulfite aqueous solution into the reaction solution after the reaction is finished, quenching, dropwise adding hydrochloric acid to adjust the pH value to 5-6, extracting by using an extractant, and separating to obtain an iodo intermediate;
(2) adding the iodo intermediate, imidazole, cesium carbonate and cuprous iodide into a solvent, reacting at 100 ℃ and 150 ℃ for 24-72h, cooling to room temperature after the reaction is finished, adding water and an extracting agent for extraction, and separating an organic phase after drying by using a drying agent to obtain an intermediate product, namely, o-mercaptoarylimidazole;
(3) dissolving o-mercaptoarylimidazole and bromohydrocarbon in toluene, heating and refluxing for 12-18h, removing the solvent after the reaction is finished, and recrystallizing the crude product to obtain the o-mercaptoarylimidazole salt.
Taking the preparation of the compound of formula I as an example, the reaction equation is shown below:
Figure BDA0001232018210000041
Figure BDA0001232018210000051
the alkali in the step (1) of the present invention is selected from potassium hydroxide and/or sodium hydroxide, and the amount of the alkali is 2 to 6 times of the molar amount of the corresponding mercapto-substituted aromatic compound.
The alcohol in step (1) of the present invention is one or more selected from methanol, ethanol and ethylene glycol.
The dosage of iodine in the step (1) of the invention is 1 to 1.2 times of the molar weight of the corresponding sulfhydryl-substituted aromatic compound.
The amount of the sodium sulfite used in the step (1) of the present invention is 1 to 1.5 times of the molar amount of the corresponding mercapto-substituted aromatic compound.
The extractant in the step (1) is selected from one or more of dichloromethane, ethyl acetate and chloroform.
The dosage of the imidazole in the step (2) is 1 to 1.5 times of the molar quantity of the iodo intermediate.
The dosage of cesium carbonate in the step (2) of the invention is 1.5-2.0 times of the molar quantity of the iodo intermediate.
The dosage of the cuprous iodide in the step (2) is 5-10% of the molar quantity of the iodo intermediate.
The solvent in step (2) of the present invention is selected from dimethyl sulfoxide and/or N, N-dimethylformamide.
The extractant in the step (2) is selected from one or more of dichloromethane, ethyl acetate and chloroform.
The drying agent in the step (2) of the present invention is selected from anhydrous sodium sulfate and/or anhydrous magnesium sulfate.
The dosage of the brominated hydrocarbon in the step (3) is 1.0 to 2.0 times of the molar weight of the o-mercaptoarylimidazole.
The recrystallization in step (3) of the present invention uses a mixed solvent of a benign solvent and a poor solvent, and preferably may be a mixed solvent of dichloromethane/diethyl ether, methanol/toluene, ethyl acetate/n-hexane, etc.
The component (B) in the present invention is preferably an acetate or chloride of nickel, palladium, platinum, and more preferably an acetate of nickel, palladium, platinum.
The preparation method of the o-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst comprises the following steps: adding the component (A) and silver oxide into an organic solvent, stirring at room temperature, reacting for 6-18h in a dark place, filtering after the reaction is finished to obtain an organic phase, adding the component (B) into the organic phase, and continuously stirring for 36-72 h. And after the reaction is finished, filtering and removing the solvent, and recrystallizing the obtained crude product to obtain the catalyst.
The amount of the silver oxide used in the present invention is 1.5 to 3.0 times the molar amount of the component (a).
The organic solvent in the preparation method of the catalyst is selected from dichloromethane and the like.
In the method for preparing the catalyst, a mixed solvent of a benign solvent and a poor solvent is used for recrystallization, and preferably, the mixed solvent can be dichloromethane/n-hexane, methanol/toluene, ethyl acetate/diethyl ether and the like.
The o-mercapto aryl N-heterocyclic carbene metal complex catalyst can be used in combination with phosphorus compounds such as tributylphosphine and the like according to a certain proportion, and the mass ratio of the catalyst to the phosphorus compounds such as the tributylphosphine is (1-100): (0-99).
The catalyst of the invention has the application of catalyzing diisocyanate to carry out self-polymerization reaction to prepare a polyisocyanate curing agent with controllable molecular weight distribution. The diisocyanate is aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate, preferably Hexamethylene Diisocyanate (HDI), Pentamethylene Diisocyanate (PDI), 4' -dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate (H)6XDI), Toluene Diisocyanate (TDI) and Xylylene Diisocyanate (XDI), more preferably Toluene Diisocyanate (TDI). The above substances can be used as the starting materials for the trimerization reaction individually or in a certain ratio.
In the present invention, the catalyst is added in portions or at once, and the amount of the catalyst is 20 to 1000ppm, preferably 50 to 500ppm, more preferably 50 to 200ppm, based on the mass of the diisocyanate.
Preferably, the catalyst is used for the preparation of a TDI trimer, comprising the steps of: mixtures of TDI-80 (Vanhua chemical group Co., Ltd.) and solvents, N2Protecting, heating to 40-60 deg.C, and keeping the temperature for 1-2 h. Adding the composite of the catalyst and the solvent synthesized by the invention in batches, controlling the reaction temperature at 40-80 ℃, monitoring the NCO value of the product after the reaction is started, adding a polymerization inhibitor to terminate the reaction after the NCO value reaches a specific range, testing the free monomer content, viscosity and molecular weight distribution of the product without a subsequent separation process, and discharging after the requirement is met. The solvent is one or a combination of more of ethyl acetate, butyl acetate and dimethyl carbonate and is dehydrated in advance; the content of TDI-80 in the mixture of TDI-80 and solvent is 46-54 wt%; the catalyst and solvent composition, the catalyst content accounts for 6-10 wt%; the polymerization inhibitor is one of phosphoric acid, hypophosphorous acid or benzoyl chloride, and the dosage of the polymerization inhibitor is 1-1.5 times of the molar weight of the catalyst.
The invention has the positive effects that: (1) the invention starts from the design of the catalyst, the catalyst is modified to have certain steric hindrance, and the steric hindrance effect is utilized to promote the reaction between small molecules and inhibit the reaction between large molecules and small molecules or between large molecules, so that the product with excellent molecular weight distribution is obtained. (2) The existing industrial preparation of TDI trimer curing agent adopts a chemical method, and the method has the defects that the obtained product is often high in molecular weight distribution, especially high polymer content, and influences downstream application, for example, the high polymer content causes poor compatibility of the curing agent and resin, and the gloss of a paint film formed by the curing agent and the resin is poor. The synthesized catalyst can obtain TDI tripolymer curing agent with relatively low high polymer content and excellent molecular weight distribution by adjusting substituent groups. All percentages referred to in the present invention are mass percentages unless otherwise specified.
Detailed Description
The diisocyanate monomer is degassed for 30min under the condition of stirring at 100Pa without special description, and N is adopted in the reaction process after degassing2And (4) protecting.
The NCO content is measured according to the method of GB/T12009.4-1989.
The kinetic viscosity designed by the invention is obtained by using a Brookfield DV-I Prime viscometer and an S21 rotor at 25 ℃.
The trimer molecular weight distribution described in the present invention was characterized by Waters (1515/2707/2414) molecular gel chromatography.
The reagents used in the synthesis of the present invention were purchased from Sigma-Aldrich.
The nuclear magnetic analysis of the catalyst ligand synthesized by the method is characterized by adopting Bruker 400MHZ Advance. The high resolution mass spectrum is characterized by using Thermo Q active Focus/Ultimate 3000.
Example 1
Preparation of catalyst # 1
5.5 parts of 2, 4-dichlorothiophenol and 3.5 parts of potassium hydroxide are dissolved in 54 parts of methanol, 7.6 parts of iodine is dissolved in 45 parts of methanol and added into the system drop by drop at room temperature, and the reaction is continued for 1.5h after the addition is finished. After the reaction is finished, 3.8 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of dichloromethane is added into the system for extraction and organic phase is retained after the pH value is adjusted to 5, and the solvent is removed under reduced pressure to obtain 2, 4-dichloro-6-iodothiophenol
Figure BDA0001232018210000081
9.2 parts of 2, 4-dichloro-6-iodothiophenol, 2.5 parts of imidazole, 14 parts of cesium carbonate and 0.3 part of cuprous iodide are added into 120 parts of dimethyl sulfoxide and reacted for 36 hours at 120 ℃. After completion of the reaction, the system was cooled to room temperature, 100 parts of water and 100 parts of methylene chloride were added to conduct extraction and the organic phase was retained, followed by drying with 20 parts of anhydrous sodium sulfateDrying, and removing solvent under reduced pressure to obtain 2-mercapto-3, 5-dichlorophenyl-imidazole
Figure BDA0001232018210000082
7.5 parts of 2-mercapto-3, 5-dichlorophenyl-imidazole and 9.6 parts of 2,4, 6-trimethylphenyl bromomethane are dissolved in 100 parts of toluene, heated and refluxed for 15 hours, the solvent is removed under reduced pressure after the reaction is finished, and the crude product is recrystallized in dichloromethane/diethyl ether to obtain a white solid with the yield of about 85 percent.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:
1H NMR(CDCl3,400MHz):9.14(1H,s),7.45(1H,s),7.36(1H,s),7.30(1H,s),6.95(1H,s),6.94(2H,s),5.59(2H,s),2.39(6H,s),2.31(3H,s)；
13C NMR(CDCl3,100MHz):150.5,150.1,147.5,134.1,138.9,136.8,129.9,126.4,125.4,125.3,123.7,121.9,119.9,48.6,35.8,34.7；
HRMS(ESI):Calcd for C19H19Cl2N2S[M-Br]+378.3380,Found:378.3376。
in a synthesis kettle, 13.5 parts of N- (2-mercapto-3, 5-dichlorophenyl) -N '- (2', 4 ', 6' -trimethylphenyl) methyl-imidazole bromide salt and 20 parts of silver oxide are added into 100 parts of dichloromethane, stirred at room temperature and reacted in a dark place for 12 hours, an organic phase is obtained after the reaction is finished and filtered, and 6.7 parts of palladium acetate is added into the organic phase and continuously stirred for 48 hours. After the reaction was completed, the solvent was removed by filtration and reduced pressure, and the obtained crude product was recrystallized in methylene chloride/n-hexane to obtain colorless crystals with a yield of about 70%. The ligand complex structure of catalyst # 1 is as follows:
Figure BDA0001232018210000091
example 2
Preparation of catalyst # 2
Dissolving 7 parts of 2, 4-dimethylthiophenol and 7 parts of potassium hydroxide in 54 parts of methanol, dissolving 13 parts of iodine in 45 parts of methanol, dropwise adding the solution to the system at room temperature,after the dropwise addition, the reaction was continued for 1 hour. After the reaction is finished, 7.6 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of ethyl acetate is added into the system for extraction and organic phase is remained after the pH value is adjusted to 5, and the solvent is removed under reduced pressure to obtain 4, 6-dimethyl-2-iodothiophenol
Figure BDA0001232018210000101
10.5 parts of 4, 6-dimethyl-2-iodothiophenol, 4.0 parts of imidazole, 25.9 parts of cesium carbonate and 0.6 part of cuprous iodide are added into 120 parts of dimethyl sulfoxide and reacted for 24 hours at 100 ℃. After the reaction is finished, cooling the system to room temperature, adding 100 parts of water and 100 parts of ethyl acetate for extraction, keeping an organic phase, drying the mixture by using 20 parts of anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain the 2-mercapto-3, 5-dimethylphenyl-imidazole
Figure BDA0001232018210000102
8.7 parts of 2-mercapto-3, 5-dimethylphenyl-imidazole and 9.6 parts of 2,4, 6-trimethylphenyl bromomethane are dissolved in 100 parts of toluene, heated and refluxed for 12 hours, the solvent is removed under reduced pressure after the reaction is finished, and the crude product is recrystallized in ethyl acetate/n-hexane to obtain a white solid with the yield of about 87 percent.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:
1H NMR(CDCl3,400MHz):9.13(1H,s),7.44(1H,s),7.35(1H,s),7.29(1H,s),6.94(1H,s),6.93(2H,s),5.58(2H,s),2.39(6H,s),2.34(3H,s),2.31(3H,s),2.15(3H,s)；
13C NMR(CDCl3,100MHz):150.5,150.1,147.5,134.1,138.9,136.8,129.9,126.4,125.4,125.3,123.7,121.9,119.9,48.6,35.8,34.7,21.7,16.9；
HRMS(ESI):Calcd for C21H25N2S[M-Br]+337.1733,Found:337.1735。
in a synthesis kettle, 15 parts of N- (2-mercapto-3, 5-dimethylphenyl) -N '- (2', 4 ', 6' -trimethylphenyl) methyl-imidazole bromide salt and 27 parts of silver oxide are added into 100 parts of dichloromethane, stirred at room temperature, reacted in a dark place for 6 hours, filtered after the reaction is finished to obtain an organic phase, and 6.7 parts of palladium acetate is added into the organic phase and continuously stirred for 36 hours. After completion of the reaction, the solvent was removed by filtration and reduced pressure, and the obtained crude product was recrystallized from ethyl acetate/diethyl ether to give colorless crystals with a yield of about 75%. The ligand complex structure of catalyst # 2 is as follows:
Figure BDA0001232018210000111
example 3
Preparation of No. 3 catalyst
5.0 parts of 4-tert-butyl thiophenol and 7 parts of sodium hydroxide are dissolved in 54 parts of ethylene glycol, 9 parts of iodine is dissolved in 45 parts of ethylene glycol and is added into the system drop by drop at room temperature, and the reaction is continued for 3 hours after the addition is finished. After the reaction is finished, 5.7 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of dichloromethane is added into the system for extraction and organic phase is retained after the pH value is adjusted to 6, and the solvent is removed under reduced pressure to obtain 4-tert-butyl-2-iodothiophenol
Figure BDA0001232018210000112
8.8 parts of 4-tert-butyl-2-iodothiophenol, 2.5 parts of imidazole, 15.7 parts of cesium carbonate and 0.57 part of cuprous iodide were added to 120 parts of N, N' -dimethylformamide and reacted at 150 ℃ for 72 hours. After the reaction is finished, cooling the system to room temperature, adding 100 parts of water and 100 parts of chloroform for extraction, reserving an organic phase, drying the organic phase by using 20 parts of anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain the 2-mercapto-5-tert-butylphenyl-imidazole
Figure BDA0001232018210000113
7.0 parts of 2-mercapto-5-tert-butylphenyl imidazole and 9.6 parts of 2,4, 6-trimethylphenyl bromomethane are dissolved in 100 parts of toluene, heated under reflux for 18h, after the reaction is complete, the solvent is removed under reduced pressure, and the crude product is recrystallized from dichloromethane/diethyl ether to give a white solid in a yield of about 87%.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:1H NMR(CDCl3,400MHz):9.55(1H,s),9.46(1H,s),7.53(1H,dd),7.43(1H,s),7.24(1H,s),7.22(1H,s),7.15(1H,d,J＝7.3Hz),6.90(2H,s),5.67(2H,s),2.27(9H,s),1.24(9H,s)；
13C NMR(CDCl3,100MHz):147.9,143.8,140.0,138.3,135.8,130.0,129.0,128.5,128.2,125.3,125.2,123.2,121.4,121.0,121.0,118.8,48.5,34.3,31.4,21.1,19.9；
HRMS(ESI):Calcd for C23H29N2S[M-Br]+365.2046,Found:365.2045。
in a synthesis kettle, 13.4 parts of N- (2-mercapto-5-tert-butylphenyl) -N '- (2', 4 ', 6' -trimethylphenyl) methyl-imidazole bromide salt and 30 parts of silver oxide are added into 100 parts of dichloromethane, stirred at room temperature, reacted in a dark place for 18 hours, filtered after the reaction is finished to obtain an organic phase, and 6.7 parts of palladium acetate is added into the organic phase and continuously stirred for 72 hours. After the reaction was completed, the solvent was removed by filtration and reduced pressure, and the obtained crude product was recrystallized in methylene chloride/n-hexane to obtain colorless crystals with a yield of about 73%. The ligand complex structure of catalyst # 3 is as follows:
Figure BDA0001232018210000121
example 4
Preparation of catalyst # 4
Dissolving 7.0 parts of 4-acetamino thiophenol and 7 parts of potassium hydroxide in 54 parts of methanol, dissolving 12.7 parts of iodine in 45 parts of methanol, dropwise adding into the system at room temperature, and continuing to react for 2 hours after the dropwise addition. After the reaction is finished, 7.5 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of chloroform is added into the system for extraction and organic phase is retained after the pH value is adjusted to 5, and the solvent is removed under reduced pressure to obtain 4-acetamido-2-iodothiophenol
Figure BDA0001232018210000131
Adding 10.5 parts of 4-acetamido-2-iodothiophenol, 3.1 parts of imidazole, 21 parts of cesium carbonate and 0.6 part of cuprous iodide into 120 parts of dimethylIn sulfoxide, react for 48h at 130 ℃. After the reaction is finished, cooling the system to room temperature, adding 100 parts of water and 100 parts of chloroform for extraction, reserving an organic phase, drying the organic phase by using 20 parts of anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain the 2-mercapto-4-acetamidophenyl-imidazole
Figure BDA0001232018210000132
9.0 parts of 2-mercapto-4-acetamidophenyl-imidazole and 9.6 parts of 2,4, 6-trimethylphenyl bromomethane were dissolved in 100 parts of toluene, heated under reflux for 12 hours, the solvent was removed under reduced pressure after the reaction was complete, and the crude product was recrystallized in methanol/toluene to give a white solid with a yield of about 86%.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:
1H NMR(CDCl3,400MHz):9.55(1H,s),9.46(1H,s),7.53(1H,dd),7.43(1H,s),7.24(1H,s),7.23(1H,br s),7.22(1H,s),7.15(1H,d,J＝7.3Hz),6.90(2H,s),5.67(2H,s),2.27(9H,s),2.04(3H,s)；
13C NMR(CDCl3,100MHz):168.9,147.9,143.8,140.0,138.3,135.8,130.0,129.0,128.5,128.2,125.3,125.2,123.2,121.4,121.0,121.0,118.8,48.5,34.3,31.4,24.0；
HRMS(ESI):Calcd for C23H29N2S[M-Br]+365.2046,Found:365.2045。
in a synthesis kettle, 15.5 parts of N- (2-mercapto-5-acetamidophenyl) -N '- (2', 4 ', 6' -trimethylphenyl) methyl-imidazole bromide salt and 35 parts of silver oxide are added into 100 parts of dichloromethane, stirred at room temperature and reacted in a dark place for 6 hours, an organic phase is obtained after the reaction is finished and filtered, 6.7 parts of palladium acetate is added into the organic phase, and the stirring is continued for 36 hours. After the reaction was complete, the solvent was removed by filtration and reduced pressure, and the crude product obtained was recrystallized in methanol/toluene to give colorless crystals with a yield of about 76%. The ligand complex structure of catalyst # 4 is as follows:
Figure BDA0001232018210000141
example 5
Preparation of No. 5 catalyst
4.3 parts of 1-naphthylthiophenol and 7 parts of potassium hydroxide are dissolved in 54 parts of ethanol, 7.6 parts of iodine is dissolved in 45 parts of ethanol and is added into the system drop by drop at room temperature, and the reaction is continued for 1.5 hours after the addition is finished. After the reaction is finished, 3.8 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of dichloromethane is added into the system for extraction and organic phase is retained after the pH value is adjusted to 5, and the solvent is removed under reduced pressure to obtain 2-iodo-1-naphthylthiophenol
Figure BDA0001232018210000142
8.0 parts of 2-iodo-1-naphthylthiophenol, 2.0 parts of imidazole, 18.2 parts of cesium carbonate and 0.53 part of cuprous iodide are added into 120 parts of dimethyl sulfoxide and reacted for 36 hours at 120 ℃. After the reaction is finished, cooling the system to room temperature, adding 100 parts of water and 100 parts of ethyl acetate for extraction, retaining an organic phase, drying the organic phase by using 20 parts of anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain beta- (alpha-mercaptonaphthyl) -imidazole
Figure BDA0001232018210000143
6.0 parts of beta- (alpha-mercaptonaphthyl) -imidazole and 9.6 parts of 2,4, 6-trimethylphenyl bromomethane are dissolved in 100 parts of toluene, heated and refluxed for 15 hours, the solvent is removed under reduced pressure after the reaction is finished, and the crude product is recrystallized in dichloromethane/diethyl ether to obtain white solid with the yield of about 86 percent.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:
1H NMR(CDCl3,400MHz):9.55(1H,s),9.46(1H,s),8.08(2H,m),7.86-7.44(5H,m),6.79(2H,s),5.67(2H,s),2.27(9H,s)；
13C NMR(CDCl3,100MHz):141.1,138.1,137.0,136.6,135.2,134.0,128.7,128.3,127.8,127.0,126.6,126.3,125.1,123.4,122.8,49.2,21.9,19.4；
HRMS(ESI):Calcd for C23H23N2S[M-Br]+359.1576,Found:359.1579。
in a synthesis kettle, 12.5 parts of N-beta- (alpha-mercaptonaphthyl) -N '- (2', 4 ', 6' -trimethylphenyl) -imidazole bromide salt and 20 parts of silver oxide are added into 100 parts of dichloromethane, stirred at room temperature and reacted away from light for 12 hours, an organic phase is obtained by filtering after the reaction is finished, and 6.7 parts of palladium acetate is added into the organic phase and continuously stirred for 48 hours. After the reaction was completed, the solvent was removed by filtration and reduced pressure, and the obtained crude product was recrystallized in methylene chloride/n-hexane to obtain colorless crystals with a yield of about 75%. The ligand complex structure of catalyst # 5 is as follows:
Figure BDA0001232018210000151
example 6
Preparation of No. 6 catalyst
Dissolving 7.0 parts of 2, 4-dimethylthiophenol and 7 parts of potassium hydroxide in 54 parts of methanol, dissolving 13 parts of iodine in 45 parts of methanol, dropwise adding the solution into the system at room temperature, and continuing to react for 1 hour after the dropwise addition. After the reaction is finished, 7.6 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of dichloromethane is added into the system for extraction and organic phase is retained after the pH value is adjusted to 5, and the solvent is removed under reduced pressure to obtain 4, 6-dimethyl-2-iodothiophenol
Figure BDA0001232018210000161
10.6 parts of 4, 6-dimethyl-2-iodothiophenol, 4.0 parts of imidazole, 25.9 parts of cesium carbonate and 0.6 part of cuprous iodide are added into 120 parts of dimethyl sulfoxide and reacted for 36 hours at 120 ℃. After the reaction is finished, cooling the system to room temperature, adding 100 parts of water and 100 parts of dichloromethane for extraction, reserving an organic phase, drying the organic phase by using 20 parts of anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain the 2-mercapto-3, 5-dimethylphenyl-imidazole
Figure BDA0001232018210000162
8.7 parts of 2-mercapto-3, 5-dimethylphenylimidazole and 7.3 parts of benzyl bromomethane are dissolved in 100 parts of toluene, the mixture is heated and refluxed for 15 hours, the solvent is removed under reduced pressure after the reaction is finished, and the crude product is recrystallized in dichloromethane/diethyl ether to obtain a white solid with the yield of about 87 percent.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:
1H NMR(CDCl3,400MHz):9.13(1H,s),7.44(1H,s),7.35(1H,s),7.29(1H,s),7.26-7.23(3H,m),6.94(1H,s),6.93(2H,s),5.58(2H,s),2.34(3H,s),2.31(3H,s)；
13C NMR(CDCl3,100MHz):150.5,150.1,147.5,134.1,138.9,136.8,129.9,126.4,125.4,125.3,123.7,121.9,119.9,48.6,21.7,21.5；
HRMS(ESI):Calcd for C18H19N2S[M-Br]+295.1263,Found:295.1261。
in a synthesis kettle, 15.0 parts of N- (2-mercapto-3, 5-dimethylphenyl) -N' -benzyl-imidazole bromide salt and 20 parts of silver oxide are added into 100 parts of dichloromethane, stirred at room temperature and reacted away from light for 12 hours, an organic phase is obtained after the reaction is finished and filtered, and 6.7 parts of palladium acetate is added into the organic phase and continuously stirred for 48 hours. After the reaction was completed, the solvent was removed by filtration and reduced pressure, and the obtained crude product was recrystallized in methylene chloride/n-hexane to obtain colorless crystals with a yield of about 75%. The ligand complex structure of catalyst # 6 is as follows:
Figure BDA0001232018210000171
example 7
Preparation of No. 7 catalyst
Dissolving 7.0 parts of 2, 4-dimethylthiophenol and 7 parts of potassium hydroxide in 54 parts of methanol, dissolving 13 parts of iodine in 45 parts of methanol, dropwise adding the solution into the system at room temperature, and continuing to react for 1 hour after the dropwise addition. After the reaction is finished, 7.6 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of dichloromethane is added into the system for extraction and organic phase is retained after the pH value is adjusted to 5, and the solvent is removed under reduced pressure to obtain 4, 6-dimethyl-2-iodothiophenol
Figure BDA0001232018210000172
4, 6-dimethyl-2-iodothiophenol10.6 parts of imidazole, 4.0 parts of imidazole, 25.9 parts of cesium carbonate and 0.6 part of cuprous iodide are added into 120 parts of dimethyl sulfoxide and reacted for 36 hours at 120 ℃. After the reaction is finished, cooling the system to room temperature, adding 100 parts of water and 100 parts of ethyl acetate for extraction, keeping an organic phase, drying the mixture by using 20 parts of anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain the 2-mercapto-3, 5-dimethylphenyl-imidazole
Figure BDA0001232018210000173
8.6 parts of 2-mercapto-3, 5-dimethylphenyl-imidazole and 8.3 parts of 1-bromobutane are dissolved in 100 parts of toluene, heated under reflux for 15h, after the reaction is complete the solvent is removed under reduced pressure and the crude product is recrystallized from ethyl acetate/n-hexane to give a white solid with a yield of about 87%.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:
1H NMR(CDCl3,400MHz):9.14(1H,s),7.42(1H,s),7.33(1H,s),7.29(1H,s),6.94(1H,s),6.93(2H,s),4.04(2H,t,J＝7.4Hz),2.34(3H,s),2.31(3H,s),1.74(2H,m),1.31(2H,m),0.90(3H,t,J＝8.0Hz)；
13C NMR(CDCl3,100MHz):147.2,142.2,138.1,125.1,124.3,124.0,123.4,121.5,47.5,33.2,22.0,21.6,20.5,13.8；
HRMS(ESI):Calcd for C15H21N2S[M-Br]+261.1420,Found:261.1425。
in a synthesis kettle, 13.0 parts of N- (2-mercapto-3, 5-dimethylphenyl) -N' -N-butyl-imidazole bromide salt and 20 parts of silver oxide are added into 100 parts of dichloromethane, stirred at room temperature and reacted in a dark place for 12 hours, an organic phase is obtained by filtering after the reaction is finished, and 6.7 parts of palladium acetate is added into the organic phase and continuously stirred for 48 hours. After the reaction was completed, the solvent was removed by filtration and reduced pressure, and the obtained crude product was recrystallized in methylene chloride/n-hexane to obtain colorless crystals with a yield of about 75%. The ligand complex structure of catalyst # 7 is as follows:
Figure BDA0001232018210000181
example 8
Preparation of catalyst # 8
Dissolving 7.0 parts of 2, 4-dimethylphenol and 7 parts of potassium hydroxide in 54 parts of methanol, dissolving 13 parts of iodine in 45 parts of methanol, dropwise adding the solution into the system at room temperature, and continuing the reaction for 1 hour after the dropwise addition. After the reaction is finished, 7.6 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of dichloromethane is added into the system for extraction and organic phase is retained after the pH value is adjusted to 5, and the solvent is removed under reduced pressure to obtain 4, 6-dimethyl-2-iodothiophenol
Figure BDA0001232018210000182
10.6 parts of 4, 6-dimethyl-2-iodothiophenol, 4.0 parts of imidazole, 25.9 parts of cesium carbonate and 0.6 part of cuprous iodide are added into 120 parts of dimethyl sulfoxide and reacted for 36 hours at 120 ℃. After the reaction is finished, cooling the system to room temperature, adding 100 parts of water and 100 parts of ethyl acetate for extraction, keeping an organic phase, drying the mixture by using 20 parts of anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain the 2-mercapto-3, 5-dimethylphenyl-imidazole
Figure BDA0001232018210000191
8.6 parts of 2-mercapto-3, 5-dimethylphenylimidazole and 7.3 parts of 1-bromopropane are dissolved in 100 parts of toluene, heated under reflux for 15h, the solvent is removed under reduced pressure after the reaction is finished, and the crude product is recrystallized in dichloromethane/diethyl ether to give a white solid with a yield of about 87%.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:
1H NMR(CDCl3,400MHz):9.12(1H,s),7.43(1H,s),7.35(1H,s),7.30(1H,s),6.95(1H,s),6.93(2H,s),4.14(2H,t,J＝7.4Hz),2.34(3H,s),2.31(3H,s),1.74(2H,m),1.29(3H,t,J＝8.0Hz)；
13C NMR(CDCl3,100MHz):147.2,142.2,138.1,125.1,124.3,124.0,123.4,121.5,47.7,33.3,21.8,21.5,19.9；
HRMS(ESI):Calcd for C14H19N2S[M-Br]+247.1263,Found:247.1259。
in a synthesis kettle, 13.0 parts of N- (2-mercapto-3, 5-dimethylphenyl) -N' -N-propyl-imidazole bromide salt and 20 parts of silver oxide are added into 100 parts of dichloromethane, stirred at room temperature and reacted away from light for 12 hours, an organic phase is obtained by filtration after the reaction is finished, and 6.7 parts of palladium acetate is added into the organic phase and continuously stirred for 48 hours. After the reaction was completed, the solvent was removed by filtration and reduced pressure, and the obtained crude product was recrystallized in methylene chloride/n-hexane to obtain colorless crystals with a yield of about 75%. The ligand complex structure of catalyst # 8 is as follows:
Figure BDA0001232018210000201
example 9
Preparation of catalyst No. 9
Dissolving 7.0 parts of 2, 4-dimethylphenol and 7 parts of potassium hydroxide in 54 parts of methanol, dissolving 13 parts of iodine in 45 parts of methanol, dropwise adding the solution into the system at room temperature, and continuing the reaction for 1 hour after the dropwise addition. After the reaction is finished, 7.6 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of dichloromethane is added into the system for extraction and organic phase is retained after the pH value is adjusted to 5, and the solvent is removed under reduced pressure to obtain 4, 6-dimethyl-2-iodothiophenol
Figure BDA0001232018210000202
10.6 parts of 4, 6-dimethyl-2-iodothiophenol, 4.0 parts of imidazole, 25.9 parts of cesium carbonate and 0.6 part of cuprous iodide are added into 120 parts of dimethyl sulfoxide and reacted for 36 hours at 120 ℃. After the reaction is finished, cooling the system to room temperature, adding 100 parts of water and 100 parts of ethyl acetate for extraction, keeping an organic phase, drying the mixture by using 20 parts of anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain the 2-mercapto-3, 5-dimethylphenyl-imidazole
Figure BDA0001232018210000203
8.6 parts of 2-mercapto-3, 5-dimethylphenyl-imidazole and 8.3 parts of 2-bromobutane are dissolved in 100 parts of toluene and heated under reflux for 15h, after the reaction is complete the solvent is removed under reduced pressure and the crude product is recrystallized from dichloromethane/diethyl ether to give a white solid in about 82% yield.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:
1H NMR(CDCl3,400MHz):9.12(1H,s),7.43(1H,s),7.35(1H,s),7.30(1H,s),6.95(1H,s),6.93(2H,s),4.05(1H,m),2.34(3H,s),2.31(3H,s),1.77(2H,m),1.67(2H,d,J＝7.0Hz),0.91(3H,t,J＝8.0Hz)；
13C NMR(CDCl3,100MHz):147.2,142.2,138.1,125.1,124.3,124.0,123.4,121.5,57.7,32.7,22.6,21.6,21.5,11.5；
HRMS(ESI):Calcd for C15H21N2S[M-Br]+261.1420,Found:261.1421。
adding 13.0 parts of N- (2-mercapto-3, 5-dimethylphenyl) -N' -isobutyl-imidazole bromide salt and 20 parts of silver oxide into 100 parts of dichloromethane in a synthesis kettle, stirring at room temperature, reacting for 12 hours in a dark place, filtering after the reaction is finished to obtain an organic phase, adding 6.7 parts of palladium acetate into the organic phase, and continuing stirring for 48 hours. After the reaction was completed, the solvent was removed by filtration and reduced pressure, and the obtained crude product was recrystallized in methylene chloride/n-hexane to obtain colorless crystals with a yield of about 78%. The ligand complex structure of catalyst # 9 is as follows:
Figure BDA0001232018210000211
example 10
Preparation of catalyst # 10
5.7 parts of 2-methylfuran-3-thiophenol and 7 parts of potassium hydroxide are dissolved in 54 parts of methanol, 13 parts of iodine is dissolved in 45 parts of methanol and is added into the system drop by drop at room temperature, and the reaction is continued for 1 hour after the addition is finished. After the reaction is finished, 7.6 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of ethyl acetate is added into the system for extraction and organic phase is remained after the pH value is adjusted to 5, and the solvent is removed under reduced pressure to obtain 4-iodine-2-methylfuran-3-thiophenol
Figure BDA0001232018210000212
9.5 parts of 4-iodine-2-methylfuran-3-thiophenol, 4.0 parts of imidazole, 25.9 parts of cesium carbonate and 0.6 part of cuprous iodide are added into 120 parts of dimethyl sulfoxide and reacted for 24 hours at 100 ℃. After the reaction is finished, cooling the system to room temperature, adding 100 parts of water and 100 parts of ethyl acetate for extraction, keeping an organic phase, drying the mixture by using 20 parts of anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain the N- [4- (2-methyl-3-mercapto) furyl]-an imidazole of the structure
Figure BDA0001232018210000221
Dissolving 7.6 parts of the substituted imidazole and 9.6 parts of 2,4, 6-trimethylphenyl bromomethane in 100 parts of toluene, heating and refluxing for 12 hours, removing the solvent under reduced pressure after the reaction is finished, and recrystallizing the crude product in ethyl acetate/n-hexane to obtain a white solid with the yield of about 86%.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:
1H NMR(CDCl3,400MHz):8.92(1H,s),7.75(1H,s),7.65(1H,s),7.58(1H,s),6.79(2H,s),5.96(2H,s),2.35(6H,s),2.34(3H,s),2.30(3H,s)；
13C NMR(CDCl3,100MHz):151.0,142.3,137.0,136.6,136.1,135.2,135.1,127.8,123.0,115.7,106,51.1,19.4,9.8,21.9；
HRMS(ESI):Calcd for C18H21N2OS[M-Br]+392.0558,Found:392.0553。
in a synthesis kettle, 14 parts of synthesized N- [4- (2-methyl-3-mercapto) furyl ] -N '- (2', 4 ', 6' -trimethylphenyl) -imidazole bromide salt and 27 parts of silver oxide are added into 100 parts of dichloromethane, stirred at room temperature and reacted in a dark place for 6 hours, an organic phase is obtained after the reaction is finished and filtered, 6.7 parts of palladium acetate is added into the organic phase, and the stirring is continued for 36 hours. After completion of the reaction, the solvent was removed by filtration and reduced pressure, and the obtained crude product was recrystallized from ethyl acetate/diethyl ether to give colorless crystals with a yield of about 78%. The ligand complex structure of catalyst # 10 is as follows:
Figure BDA0001232018210000222
example 11
Preparation of catalyst # 11
5.8 parts of thiophene-2-thiophenol and 7 parts of potassium hydroxide are dissolved in 54 parts of methanol, 13 parts of iodine is dissolved in 45 parts of methanol and is added into the system drop by drop at room temperature, and the reaction is continued for 1 hour after the addition is finished. After the reaction is finished, 7.6 parts of sodium sulfite is dissolved in 30 parts of water and added into the reaction solution for quenching, hydrochloric acid is added dropwise to adjust the pH value, 80 parts of ethyl acetate is added into the system for extraction and organic phase is remained after the pH value is adjusted to 5, and the solvent is removed under reduced pressure to obtain 3-iodothiophene-2-thiophenol
Figure BDA0001232018210000231
9.6 parts of 4-iodine-2-methylfuran-3-thiophenol, 4.0 parts of imidazole, 25.9 parts of cesium carbonate and 0.6 part of cuprous iodide are added into 120 parts of dimethyl sulfoxide and reacted for 24 hours at 100 ℃. After the reaction is finished, cooling the system to room temperature, adding 100 parts of water and 100 parts of ethyl acetate for extraction, retaining an organic phase, drying the organic phase by using 20 parts of anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain the N- [3- (2-mercapto) thienyl]-an imidazole of the structure
Figure BDA0001232018210000232
Dissolving 7.7 parts of the substituted imidazole and 9.6 parts of 2,4, 6-trimethylphenyl bromomethane in 100 parts of toluene, heating and refluxing for 12 hours, removing the solvent under reduced pressure after the reaction is finished, and recrystallizing the crude product in ethyl acetate/n-hexane to obtain a white solid with the yield of about 88 percent.
Nuclear magnetic and mass spectrometric analysis of the product were as follows:
1H NMR(CDCl3,400MHz):8.95(1H,s),7.76(1H,s),7.68(1H,s),7.62 1H,d,J＝7.5Hz),7.05(1H,d,J＝7.5Hz),6.78(2H,s),5.96(2H,s),2.34(6H,s),2.33(3H,s)；
13C NMR(CDCl3,100MHz):146.5,137.0,136.6,136.1,135.2,127.8,127.2,125.8,123.5,123.0,115.7,51.1,21.9,19.4；
HRMS(ESI):Calcd for C17H19N2S2[M-Br]+315.0984,Found:315.0986。
in a synthesis kettle, 14 parts of synthesized N- [3- (2-mercapto) thienyl ] -N '- (2', 4 ', 6' -trimethylphenyl) -imidazole bromide salt and 27 parts of silver oxide are added into 100 parts of dichloromethane, stirred at room temperature, reacted for 6 hours in a dark place, filtered after the reaction is finished to obtain an organic phase, and 6.7 parts of palladium acetate is added into the organic phase and continuously stirred for 36 hours. After completion of the reaction, the solvent was removed by filtration and reduced pressure, and the obtained crude product was recrystallized from ethyl acetate/diethyl ether to give colorless crystals with a yield of about 77%. The ligand complex structure of catalyst # 11 is as follows:
Figure BDA0001232018210000241
examples 12 to 22
Preparation of TDI trimer
In the synthesis kettle, 1000 parts of TDI-80 and 1000 parts of butyl acetate are added in one time according to the weight ratio of the formula. The reaction system was warmed to 60 ℃. The catalyst was diluted with butyl acetate to a concentration of 10% by weight and added dropwise to the reaction system. The change of NCO content was detected during the reaction, and when the NCO content reached 8.0 wt%, phosphoric acid in an amount equimolar to the catalyst was added to the system to terminate the reaction. The trimer product obtained was tested for free monomer content, viscosity and molecular weight distribution (mainly for detecting the content of high polymers, which is a generic term for polymers with a molecular weight higher than that of nonamers in molecular gel chromatography). Catalysts # 1-11 correspond to examples 12-22, respectively. The reaction conditions and results are shown in Table 1.
Example 23
Synthesis of TDI trimer by compound catalytic system
In the synthesis kettle, 1000 parts of TDI-80 and 1000 parts of butyl acetate are added in one time according to the weight ratio of the formula. The reaction system was warmed to 60 ℃. 0.08 parts of catalyst # 2 and 0.04 parts of tributylphosphine diluted with butyl acetate to a concentration of 10% were added dropwise to the reaction system. The change in the NCO% value was measured during the reaction, and when the NCO% value reached 8.0 wt%, phosphoric acid in an amount equimolar to the catalyst was added to the system to terminate the reaction. The trimer product obtained was tested for free monomer content, viscosity and molecular weight distribution. The reaction conditions and results are shown in Table 1.
Comparative example
Preparation of TDI trimer
In the synthesis kettle, 800 parts of TDI-80 and 800 parts of butyl acetate are added at one time according to the weight ratio of the formula. The reaction system was warmed to 60 ℃. 1.2 parts of a Mannich base catalyst was added dropwise to the reaction system. Detecting the change of the NCO% value in the reaction process, reacting for 26h, wherein the NCO% value is 8.0 wt%, and adding methyl p-toluenesulfonate into the system to terminate the reaction. The trimer product obtained was tested for free monomer content, viscosity and molecular weight distribution (mainly for high polymer content). The reaction conditions and results are shown in Table 1.
Figure BDA0001232018210000251
TABLE 1 reaction conditions and results of examples 12-23 and comparative examples
Figure BDA0001232018210000252
Figure BDA0001232018210000261
Comparison of the comparative example with the examples shows that: the catalyst is modified to have certain steric hindrance, and the steric hindrance effect is utilized to promote the reaction between small molecules and inhibit the reaction between large molecules and small molecules or between large molecules, so that a product with excellent molecular weight distribution can be obtained. The o-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst is applied to the synthesis of polyisocyanate, not only solves the problem of high polymer in the direct chemical synthesis method of curing agent, but also can ensure that the free monomer in the product is below 0.3 wt%.

Claims (15)

1. An o-mercapto aryl nitrogen heterocyclic carbene metal complex catalyst is prepared from the following components: (A) ortho-mercaptoarylimidazolium salts and (B) transition metal salts.
2. The catalyst according to claim 1, wherein the mass ratio of (a) to (B) is (20-55): (45-80).
3. The catalyst according to claim 1 or 2, wherein (A) the ortho-mercaptoarylimidazolium salt is selected from one or more compounds of the formulae I, II, III and IV,
Figure FDA0002585728440000011
wherein R is1Is hydrogen, halogen, alkyl or alkoxy; r2Is halogen, alkyl, alkoxy or acetylamino; r3Is alkyl, cycloalkyl or benzyl.
4. The catalyst of claim 3, wherein R is1Is halogen or alkyl of C1-C10; r2Is halogen or alkyl of C1-C10; r3Is benzyl.
5. The catalyst of claim 4, wherein R is1Is C1-C10 alkyl; r2Is C1-C10 alkyl.
6. The catalyst of claim 1, wherein the (A) ortho-mercaptoarylimidazolium salt is selected from the group consisting of N- (2-mercapto-5-tert-butylphenyl) -N ' - (2 ', 4 ', 6 ' -trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-5-acetamidophenyl) -N ' - (2 ', 4 ', 6 ' -trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-5-methoxyphenyl) -N ' - (2 ', 4 ', 6 ' -trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-5-bromophenyl) -N ' - (2 ', 4 ', 6 '-trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-3, 5-dimethylphenyl) -N' - (2 ', 4', 6 '-trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-3, 5-difluorophenyl) -N' - (2 ', 4', 6 '-trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-3, 5-dichlorophenyl) -N' - (2 ', 4', 6 '-trimethylphenyl) methyl-imidazolium bromide, N- (2-mercapto-3, 5-dimethylphenyl) -N' -benzyl-imidazolium bromide, N- (2-mercapto-3, 5-dimethylphenyl) -N ' -N-butyl-imidazole bromide salt, N- (2-mercapto-3, 5-dimethylphenyl) -N ' -isobutyl-imidazole bromide salt, N- (2-mercapto-3, 5-dimethylphenyl) -N ' -N-propyl-imidazole bromide salt, N-beta- (. alpha. -mercaptonaphthyl) -N ' - (2 ', 4 ', 6 ' -trimethylphenyl) imidazole bromide salt, N- [4- (2-methyl-3-mercapto) furyl ] -N ' - (2 ', 4 ', 6 ' -trimethylphenyl) -imidazole bromide salt and N- [3- (2-mercapto) thienyl ] -N ' - (2 ', one or more of 4 ', 6' -trimethylphenyl) -imidazole brominating salts.
7. The catalyst according to claim 1, wherein the (a) ortho-mercaptoarylimidazolium salt is prepared by a process comprising the steps of: (1) dissolving corresponding sulfhydryl substituted aromatic compound and alkali in alcohol, dropwise adding iodine alcoholic solution into the system at room temperature, continuing to react for 1-3h after dropwise adding, adding sodium sulfite aqueous solution into the reaction solution after the reaction is finished, quenching, adjusting pH to 5-6, and separating to obtain an iodo intermediate after extraction;
(2) adding the iodo intermediate, imidazole, cesium carbonate and cuprous iodide into a solvent, reacting at 100-150 ℃ for 24-72h, drying an organic phase, and separating to obtain an intermediate product, namely o-mercaptoarylimidazole;
(3) dissolving o-mercaptoarylimidazole and bromohydrocarbon in toluene, heating and refluxing for 12-18h, and performing post-treatment to obtain o-mercaptoarylimidazole salt.
8. The catalyst according to claim 1, wherein the component (B) is selected from one or more of nickel, palladium, acetate and chloride of platinum.
9. The catalyst according to claim 8, wherein the component (B) is selected from one or more of the group consisting of nickel, palladium, platinum acetates.
10. A method of preparing the catalyst of any one of claims 1-9, comprising the steps of: adding the component (A) and silver oxide into an organic solvent, stirring at room temperature, reacting for 6-18h in a dark place, filtering after the reaction is finished to obtain an organic phase, adding the component (B) into the organic phase, and continuously stirring for 36-72h to obtain the catalyst.
11. Use of the catalyst of any one of claims 1-9 or the catalyst prepared according to the process of claim 10 for catalyzing the self-polymerization of diisocyanates for the preparation of polyisocyanates.
12. Use according to claim 11, characterized in that the catalyst is used in an amount of 20 to 1000ppm, based on the mass of diisocyanate.
13. Use according to claim 12, characterized in that the catalyst is used in an amount of 50 to 500ppm, based on the mass of diisocyanate.
14. Use according to claim 13, characterized in that the catalyst is used in an amount of 50 to 200ppm, based on the mass of diisocyanate.
15. Use according to claim 11, wherein the catalyst is used for catalyzing the self-polymerization of toluene diisocyanate to produce toluene diisocyanate trimer.
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US5955609A (en) * 1997-12-31 1999-09-21 Bayer Corporation Trimer catalyst system for aliphatic and aromatic isocyanates
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CN1470509A (en) * 2002-07-03 2004-01-28 Method for preparing TDI tripolymer with low monomer content
CN101239987A (en) * 2008-01-23 2008-08-13 湖北德邦化工新材料有限公司 Siloxane modifying polyisocyanate trimer curing agent containing sulphydryl or hydroxyl
CN101531641A (en) * 2008-03-14 2009-09-16 拜尔材料科学股份公司 Preparation of polyisocyanates of the trimer type
CN105032490A (en) * 2015-07-17 2015-11-11 华南理工大学 Complex catalyst and application thereof to preparation of mixed diisocyanate trimer
CN105566239A (en) * 2015-12-16 2016-05-11 青岛科技大学 Preparation method of aliphatic diisocyanate tripolymer curing agent

Patent Citations (7)

* Cited by examiner, † Cited by third party
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JP3347414B2 (en) * 1992-09-02 2002-11-20 ビーエーエスエフ アクチェンゲゼルシャフト Method for producing low-viscosity polyisocyanate mixture containing isocyanurate groups and urethane groups
US5955609A (en) * 1997-12-31 1999-09-21 Bayer Corporation Trimer catalyst system for aliphatic and aromatic isocyanates
CN1470509A (en) * 2002-07-03 2004-01-28 Method for preparing TDI tripolymer with low monomer content
CN101239987A (en) * 2008-01-23 2008-08-13 湖北德邦化工新材料有限公司 Siloxane modifying polyisocyanate trimer curing agent containing sulphydryl or hydroxyl
CN101531641A (en) * 2008-03-14 2009-09-16 拜尔材料科学股份公司 Preparation of polyisocyanates of the trimer type
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