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CN108530331B - Method for catalyzing the addition reaction of phenyl isocyanate or phenyl isothiocyanate and thiol - Google Patents

Method for catalyzing the addition reaction of phenyl isocyanate or phenyl isothiocyanate and thiol Download PDF

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CN108530331B
CN108530331B CN201810488198.0A CN201810488198A CN108530331B CN 108530331 B CN108530331 B CN 108530331B CN 201810488198 A CN201810488198 A CN 201810488198A CN 108530331 B CN108530331 B CN 108530331B
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CN108530331A (en
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陆澄容
陆语欣
赵蓓
胡黎娟
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
    • C07C333/08—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/18—Esters of dithiocarbamic acids
    • C07C333/24—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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Abstract

本发明涉及一种催化异氰酸苯酯或异硫氰酸苯酯和硫醇加成反应的方法，包括以下步骤：将式(1)所示的异氰酸苯酯或异硫氰酸苯酯与式(2)所示的硫醇在催化剂稀土胺化物的催化作用下，在10‑75℃下反应，得到式(3)所示的硫代氨基甲酸酯类化合物，反应路线如下：

Figure DDA0001667308880000011
其中，R1和R3独立地选自C1‑C6烷基、卤素、C1‑C6烷氧基、硝基或三氟甲基；X为氧原子或硫原子；R2为取代苄基、呋喃甲基、环己基或三苯甲基，取代苄基上的取代基团为C1‑C6烷基、卤素或C1‑C6烷氧基；稀土胺化物的分子式为RE[N(SiMe3)2]3，其中RE为稀土金属元素。本发明的方法原料简单易得，操作简便，反应条件较为温和，产率较高，且底物适用范围较广。The invention relates to a method for catalyzing the addition reaction of phenyl isocyanate or phenyl isothiocyanate and thiol, comprising the following steps: adding the phenyl isocyanate or benzene isothiocyanate shown in formula (1) The ester and the thiol shown in the formula (2) are reacted at 10-75 ° C under the catalysis of the catalyst rare earth aminate to obtain the thiocarbamate compound shown in the formula (3). The reaction scheme is as follows:
Figure DDA0001667308880000011
Wherein, R 1 and R 3 are independently selected from C 1 -C 6 alkyl, halogen, C 1 -C 6 alkoxy, nitro or trifluoromethyl; X is an oxygen atom or a sulfur atom; R 2 is a substituted Benzyl, furanmethyl, cyclohexyl or trityl, the substituent on the substituted benzyl group is C 1 -C 6 alkyl, halogen or C 1 -C 6 alkoxy; the molecular formula of rare earth amine compound is RE [N(SiMe 3 ) 2 ] 3 , wherein RE is a rare earth metal element. The method of the invention has simple and easy-to-obtain raw materials, simple and convenient operation, mild reaction conditions, high yield, and wide application range of substrates.

Description

Method for catalyzing addition reaction of phenyl isocyanate or phenyl isothiocyanate and mercaptan
Technical Field
The invention relates to the field of organic chemistry, in particular to a method for catalyzing addition reaction of phenyl isocyanate or phenyl isothiocyanate and mercaptan.
Background
The thiocarbamic acid-S-ester compound has important functions in the aspect of medicine as a bactericide and antiviral; in biological aspect, the compound can be used as a biological regulator and an enzyme inhibitor; in agriculture, the compounds can be used for disinsection and weeding. Therefore, the synthesis of the thiocarbamic acid-S-ester compound has great significance in all aspects. At present, the synthesis method of the compound mainly comprises the following steps: (1) the amine firstly reacts with carbon monoxide and sulfur for carbonylation reaction, and then reacts with alkyl halide for alkylation reaction to generate a target product; (2) intramolecular rearrangement of the thiocarbonyl compound; (3) oxidative coupling reaction of amine with carbon monoxide and aromatic thiol compound; (4) selenium or palladium catalyzed amine and disulfide carbonylation reaction, dichloro compound and mercaptan carbonylation reaction, trichloro acetyl chloride and mercaptan, amine carbonylation reaction or nitro compound and carbon monoxide, mercaptan carbonylation reaction; (5) intermolecular addition reaction of thiol with isocyanate and the like.
The catalyst used in the existing intermolecular addition reaction method of phenyl isocyanate or phenyl isothiocyanate and mercaptan has larger toxicity, the application range of a substrate is narrower, and the product yield of most reactions is lower.
In addition, there are other reports of the synthesis of thiocarbamate-S-esters:
(1) in 2003, the Mizuno project group reported that the use of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) to catalyze the reaction of amines with carbon monoxide, sulfur, and alkyl halides to produce thiocarbamate-S-esters gave excellent yields under mild conditions (Mizuno, T.; Takahashi, J.; Ogawa, A. tetrahedron,2003,59, 1327-. In 2004, the subject group proposed that dimethyl sulfoxide was used as a solvent, potassium carbonate was used as a basic catalyst to catalyze the carbonylation reaction of secondary amine with carbon monoxide and sulfur, and then benzyl halohydrocarbon was added to the reaction mixture to react for 1 hour to obtain the target product. Although the yield of the reaction is good, the multi-step reaction has low utilization rate of raw materials and needs a large amount of solvent, which is not favorable for environmental protection. (Mizuno, T.; Iwai, T.; Ito, T.tetrahedron,2004,60, 2869-2873.).
(2) In 2000, the Jones task group reported that 3 equivalents of amine reacted with carbon monoxide and mercaptan using a transition metal palladium compound at room temperature for 24 hours gave a 47% yield. The by-product mainly generated in the reaction process is hydrochloride of amine, and can be directly separated; a small amount of 4-chlorophenyldiphenylphosphine was also present in the reaction, and it was found that this was obtained by reacting the triphenylphosphine dissociated in the catalyst with a thiol. (Jones, W.D.; Reynolds, K.A.; Sperry, C.K.; Lacicotte, R.J. organometallics,2000,19, 1661-1669.); in 2001, the Jones project group used nickel to catalyze the oxidative coupling of secondary amines with carbon monoxide and thiophenol to produce thiocarbamate-S-esters. Although the reaction can be carried out under mild conditions to obtain the corresponding product, the raw materials are excessive to generate certain byproducts, which is not favorable for utilization of the raw materials. At the same time, it is not suitable for primary amine substrates and primary aliphatic thiols for substrate development. (Jacob, J.; Reynolds, K.A.; Jones, W.D. organometallics,2001,20, 1028-.
(3) In 2005, the lushiwei task group proposed a method of reacting selenium-catalyzed amine with carbon monoxide and thiol at room temperature for 10 hours to produce the target product. The process uses simple and readily available starting materials and gives the desired product under mild reaction conditions, but in this paper the yields are better only for linear or less sterically hindered aliphatic mercaptans, while the yields are generally lower for aromatic mercaptans. (Zhang, X.P.; Lu, S.W.Chem.Lett.,2005,34, 606-one 607.); in 2007, the subject group discovered that the reaction of aniline with carbon monoxide and mercaptan in the presence of oxygen using 3 mmol% selenium directly catalyzed the formation of thiocarbamate S-ester, with moderate to superior yields obtained at room temperature in the absence of solvent, where the reaction did not proceed when tert-butyl mercaptan was used (Zhang, x.p.; Lu, s.w.syn.commun.,2007,37, 3291-phase 3299.); in 2008, this group used 5 mol% selenium to catalyze a one-pot reaction of nitro compounds with carbon monoxide and mercaptans at room temperature for 15 hours. Although the reaction can be carried out under relatively mild conditions, the yield of the reaction is still around 80%. If the steric hindrance of the substrate is larger, the yield of the target product is lower no matter the substrate is a nitro compound or mercaptan with large steric hindrance (Zhang, X.P.; Lu, S.W.J.chem.Res.,2008, 589-Bu 591.).
Although the above-mentioned catalytic systems can catalyze the intermolecular addition reaction of phenyl isocyanate or phenyl isothiocyanate with thiol to give thiocarbamate compounds, there are problems in these systems, such as: the raw materials are toxic, the dosage of the catalyst is large, the metal types of the catalyst are limited, the reaction conditions are harsh, the universality of substrates is poor, and the like. Therefore, it is necessary to find a preparation method with mild reaction conditions and good universality for efficiently synthesizing the thiocarbamate compound.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for catalyzing the intermolecular addition reaction of phenyl isocyanate or phenyl isothiocyanate and mercaptan, which has the advantages of simple and easily obtained raw materials, simple and convenient operation, mild reaction conditions, high yield and wide substrate application range.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for catalyzing addition reaction of phenyl isocyanate or phenyl isothiocyanate and mercaptan, which comprises the following steps:
phenyl isocyanate or phenyl isothiocyanate shown in a formula (1) and mercaptan shown in a formula (2) react at the temperature of 10-75 ℃ under the catalysis of a catalyst rare earth amide to obtain a thiocarbamate compound shown in a formula (3), and the reaction route is as follows:
Figure BDA0001667308870000031
wherein R is1And R3Independently selected from hydrogen, C1-C6Alkyl, halogen, C1-C6Alkoxy, nitro or trifluoromethyl; x is oxygen atom or sulfur atom; r2Is benzyl, substituted benzyl, furan methyl, cyclohexyl or trityl, and the substituent group on the substituted benzyl is C1-C6Alkyl, halogen or C1-C6An alkoxy group;
the molecular formula of the rare earth amide is RE [ N (SiMe)3)2]3Wherein RE is a rare earth metal element.
Further, C1-C6Alkyl is methyl, ethyl or isopropyl; halogen is fluorine, chlorine or bromine; alkoxy is methoxy, ethoxy or isopropoxy.
Preferably, R1And R3Are all hydrogen, methyl, ethylOr isopropyl, R2Is benzyl; or
R1And R3One of which is hydrogen and the other is methyl, chlorine, bromine, nitro, methoxy, ethoxy or isopropoxy, R2Is benzyl.
Preferably, R1And R3Are each hydrogen, R2Is monosubstituted substituted benzyl, and the substituent is methyl, halogen, methoxy, ethoxy or isopropoxy; or
R1And R3Are each hydrogen, R2Is a furan methyl group, a cyclohexyl group or a trityl group.
Further, the reaction time is 24-36 h.
Preferably, the reaction temperature is 10-60 ℃; more preferably, the reaction temperature is 10-40 ℃.
Furthermore, the molar ratio of phenyl isocyanate or phenyl isothiocyanate shown in the formula (1) to mercaptan shown in the formula (2) to the rare earth amide is 10-20:10-20: 0.1-1. Preferably, the molar ratio of the three components is 10:10:1, 10:10:0.5, 10:10:0.3, 10:10:0.2, 10:10:0.1, 12:10:0.1, 1:12:0.1, 15:10:0.1 and 20:10:0.1 in the above order.
Further, the reaction is carried out in a closed environment without water and oxygen and with a protective atmosphere.
Further, the protective atmosphere was an argon atmosphere.
Further, the above reaction may be carried out in the absence of a solvent or in the presence of a solvent.
Further, the reaction is carried out in an organic solvent, wherein the organic solvent is one or more of tetrahydrofuran, toluene, chlorobenzene, trichloromethane, dimethyl sulfoxide and N, N-dimethylformamide. Preferably, the organic solvent is tetrahydrofuran, toluene, chlorobenzene or chloroform.
Further, RE is selected from lanthanum, samarium, yttrium or ytterbium. I.e. the rare earth amide is preferably La [ N (SiMe)3)2]3、Sm[N(SiMe3)2]3、Y[N(SiMe3)2]3、Yb[N(SiMe3)2]3. The above catalyst may be added to the reaction vessel in the form of a solution.
Further, the method also comprises the step of quenching the reaction in air. And after the reaction is finished, exposing to air and quenching for reaction, carrying out column chromatography on the product, and carrying out spin-drying on the solvent to obtain the purified product.
By the scheme, the invention at least has the following advantages:
1. the rare earth amide compound used in the invention has high catalytic activity, the lowest dosage of the catalyst can be 1 mol% of reactant mercaptan, the product yield is higher, and the purification of the product is facilitated by using less catalyst.
2. The method has mild reaction conditions and wide reactant universality, and can efficiently catalyze the intermolecular addition reaction of the phenyliso (thio) cyanate and the mercaptan; the reaction temperature is mild, the yield of the target product is high, and the reaction operation process is simple.
3. The method is suitable for intermolecular addition reaction of various phenyl isocyanates or phenyl isothiocyanate and mercaptan, and the substrate has a wide application range.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Comparative example 1: intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 30 ℃:
108.69 μ L (1.00X 10) was added to the flask under anhydrous and oxygen-free argon shield-3Moles) phenyl isocyanate and 117.39. mu.L (1.00X 10)-3Mole) benzyl mercaptan, and the reaction was stirred in a constant temperature bath at 30 ℃. And removing the protective argon after 24 hours, and exposing to air to quench the reaction, wherein the nuclear magnetic yield is 24 percent by nuclear magnetic analysis.
Example 1: 10 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 30 ℃:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan was stirred at room temperature for 15min under argon atmosphere, and 108.69. mu.L (1.00X 10) was added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 30 ℃ for reaction. After 24 hours, removing the protective argon gas to expose and empty the quenching reaction, and obtaining the nuclear magnetic yield of 83% by nuclear magnetic analysis:1H NMR(400MHz,CDCl3)：δ7.39-7.13(m,9H,ArH),7.02(dd,J1＝19.4,J2＝12.0Hz,2H,ArH、NH),4.15(s,2H,CH2) ppm (wt.%). As can be seen from comparative example 1 and example 1, La [ N (SiMe)3)2]3When the catalyst is used as a catalyst, the final yield is greatly improved compared with the yield without using a rare earth catalyst.
Example 2:10 mol% of Sm [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 30 ℃:
0.0625g (1.00X 10 g) of the reaction flask was placed under anhydrous and oxygen-free argon atmosphere-4Mole) Sm [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan was stirred at room temperature for 15min under argon atmosphere, and 108.69. mu.L (1.00X 10) was added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 30 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 79 percent by nuclear magnetic analysis.
Example 3: 10 mol% of Yb [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 30 ℃:
0.0655g (1.00X 10) of the mixture is added into a reaction bottle under the protection of anhydrous oxygen-free argon-4Mole) Yb [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan was stirred at room temperature for 15min under argon atmosphere, and 108.69. mu.L (1.00X 10) was added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 30 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 75 percent by nuclear magnetic analysis.
Example 4: 10 mol% of Y [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 30 ℃:
0.0567g (1.00X 10 g) are added into a reaction bottle under the protection of anhydrous oxygen-free argon-4Mole) Y [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan was stirred at room temperature for 15min under argon atmosphere, and 108.69. mu.L (1.00X 10) was added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 30 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 79 percent by nuclear magnetic analysis.
Example 5:10 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 10 ℃:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan was stirred at room temperature for 15min under argon atmosphere, and 108.69. mu.L (1.00X 10) was added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 10 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 81 percent by nuclear magnetic analysis.
Example 6: 10 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 40 ℃:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan was stirred at room temperature for 15min under argon atmosphere, and 108.69. mu.L (1.00X 10) was added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 24 hours, the protective argon gas exposure is removedAir quenching reaction, and nuclear magnetic analysis shows that the nuclear magnetic yield is 86%.
Example 7: 10 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 60 ℃:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan was stirred at room temperature for 15min under argon atmosphere, and 108.69. mu.L (1.00X 10) was added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 60 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 67 percent by nuclear magnetic analysis.
Example 8: 10 mol% of La [ N (SiMe)3)2]3Catalyzing an intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 75 ℃:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan was stirred at room temperature for 15min under argon atmosphere, and 108.69. mu.L (1.00X 10) was added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 75 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 59 percent by nuclear magnetic analysis.
Example 9: 10 mol% of La [ N (SiMe)3)2]3Catalyzing an intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan in toluene:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) were added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 97 percent by nuclear magnetic analysis.
Example 10:10 mol% of La [ N (SiMe)3)2]3The intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan was catalyzed in chlorobenzene:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL chlorobenzene were stirred at room temperature for 15min under argon atmosphere, and 108.69 μ L (1.00X 10) was added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 92 percent by nuclear magnetic analysis.
Example 11: 10 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan in chloroform:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL of chloroform were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) was added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. And after 24 hours, removing the protective argon gas to expose and quench the reaction, and obtaining the nuclear magnetic yield of 89% by nuclear magnetic analysis.
Example 12:10 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan in dimethyl sulfoxide:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan and 1mL dimethyl sulfoxide were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) were further added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 22 percent by nuclear magnetic analysis.
Example 13: 10 mol% of La [ N (SiMe)3)2]3Catalyzing an intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan in N, N-dimethylformamide:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL of N, N-dimethylformamide were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) were added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and quench the reaction, and the nuclear magnetic yield is 58 percent by nuclear magnetic analysis.
Example 14: 10 mol% of La [ N (SiMe)3)2]3Catalyzing an intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan in tetrahydrofuran:
adding 0.0620g (1.00X 10) of the mixture into a reaction flask under the protection of anhydrous oxygen-free argon-4Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL tetrahydrofuran were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) were added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and quench the reaction, and the nuclear magnetic yield is 86% by nuclear magnetic analysis.
Example 15: 5 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan:
adding 0.0310g (5.00X 10) of water and oxygen under the protection of argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) were added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 98 percent by nuclear magnetic analysis.
Example 16: 3 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan:
adding 0.0186g (3.00 multiplied by 10) of the mixture into a reaction bottle under the protection of anhydrous oxygen-free argon-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) were added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 85 percent by nuclear magnetic analysis.
Example 17: 2 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan:
adding 0.0124g (2.00X 10 g) of the mixture into a reaction bottle under the protection of anhydrous oxygen-free argon-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) were added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 81 percent by nuclear magnetic analysis.
Example 18: 1 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) were added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 24 hours, the protective argon gas is removed to expose and empty the quenching reaction, and the nuclear magnetic yield is 81 percent by nuclear magnetic analysis.
Example 19: 1 mol% of La [ N (SiMe)3)2]3The intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan was catalyzed at 30 hours:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) were added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to expose and quench the reaction, and the nuclear magnetic yield is 96 percent by nuclear magnetic analysis.
Example 20:1 mol% of La [ N (SiMe)3)2]3The intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan was catalyzed at 36 hours:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) were added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 36 hours, the protective argon gas is removed to expose and quench the reaction, and the nuclear magnetic yield is 97 percent by nuclear magnetic analysis.
Comparative example 2: intermolecular addition reaction of phenylisothiocyanate and benzylthiol at 40 ℃:
119.43 mu L (1.00X 10) of the mixture is added into a reaction bottle under the protection of anhydrous oxygen-free argon-3Mols) of phenylisothiocyanate and 117.39. mu.L (1.00X 10)-3Mole) benzyl mercaptan, and the reaction was stirred in a constant temperature bath at 40 ℃. And removing the protective argon after 30 hours, and exposing to air to quench and react, wherein the nuclear magnetic yield is less than 1 percent by nuclear magnetic analysis.
Example 21: 1 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isothiocyanate and benzyl mercaptan:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan and 1mL toluene were stirred at room temperature for 15min under argon atmosphere, and 119 additional time was added.43μL(1.00×10-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. And after 30 hours, removing the protective argon, exposing and quenching to kill the reaction, and obtaining the nuclear magnetic yield of 83% by nuclear magnetic analysis. Nuclear magnetic data:1H NMR(400MHz,CDCl3)：δ8.84(s,1H,NH),7.42-7.13(m,10H,ArH),4.49(d,J＝2.3Hz,2H,CH2) ppm (wt.%). As can be seen from comparative example 2 and example 21, La [ N (SiMe)3)2]3When the catalyst is used as a catalyst, the final yield is greatly improved compared with the yield without the catalyst.
Example 22: 2 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isothiocyanate and benzyl mercaptan:
adding 0.0124g (2.00X 10 g) of the mixture into a reaction bottle under the protection of anhydrous oxygen-free argon-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 119.43. mu.L (1.00X 10) of additional toluene were added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. And after 30 hours, removing the protective argon, exposing to air and quenching to react, and obtaining the nuclear magnetic yield of 82% by nuclear magnetic analysis.
Example 23: 3 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isothiocyanate and benzyl mercaptan:
adding 0.0186g (3.00 multiplied by 10) of the mixture into a reaction bottle under the protection of anhydrous oxygen-free argon-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 119.43. mu.L (1.00X 10) of additional toluene were added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. And after 30 hours, removing the protective argon, exposing and quenching to kill the reaction, and obtaining the nuclear magnetic yield of 83% by nuclear magnetic analysis.
Example 24: 5 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of phenyl isothiocyanate and benzyl mercaptan:
under the protection of anhydrous oxygen-free argon gas0.0310g (5.00X 10) is added to the reaction flask-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 119.43. mu.L (1.00X 10) of additional toluene were added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon is removed, the reaction is quenched by air exposure, and the nuclear magnetic yield is 79 percent by nuclear magnetic analysis.
Example 25: 1 mol% of La [ N (SiMe)3)2]3Catalyzing an intermolecular addition reaction of phenyl isothiocyanate and 1.2 equivalents of benzyl mercaptan:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3Then 140.87 μ L (1.20X 10) was added-3Mol) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 119.43. mu.L (1.00X 10) of additional toluene were added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon is removed, the reaction is quenched by air exposure, and the nuclear magnetic yield is 73 percent by nuclear magnetic analysis.
Example 26: 1 mol% of La [ N (SiMe)3)2]3Catalyzing an intermolecular addition reaction of 1.2 equivalents of phenyl isothiocyanate and benzyl mercaptan:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 143.32. mu.L (1.20X 10) were added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. And after 30 hours, removing the protective argon, exposing to air, quenching and reacting, and performing nuclear magnetic analysis to obtain the nuclear magnetic yield of 89%.
Example 27: 1 mol% of La [ N (SiMe)3)2]3Catalyzing an intermolecular addition reaction of 1.5 equivalents of phenylisothiocyanate and benzylthiol:
adding 0.0062g (1.00 function) into a reaction bottle under the protection of anhydrous oxygen-free argon gas10-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 179.15. mu.L (1.50X 10) were added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. And after 30 hours, removing the protective argon, exposing to air, quenching and reacting, and performing nuclear magnetic analysis to obtain the nuclear magnetic yield of 94%.
Example 28: 1 mol% of La [ N (SiMe)3)2]3Catalyzing an intermolecular addition reaction of 2 equivalents of phenylisothiocyanate and benzylmercaptan:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 238.86. mu.L (2.00X 10) were added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. And removing the protective argon after 30 hours, and exposing to air to quench the reaction, wherein the nuclear magnetic yield is 96 percent by nuclear magnetic analysis.
As can be seen from the above examples, the rare earth amide RE [ N (SiMe) of the present invention3)2]3The method for catalyzing intermolecular addition reaction of phenyl iso (thio) cyanate and mercaptan, wherein RE is rare earth metal selected from one of lanthanum, samarium, yttrium or ytterbium, has high catalytic activity, small catalyst dosage, mild reaction conditions, wide substrate universality, high yield of target products and simple reaction operation and post-treatment process.
Example 29: 1 mol% of La [ N (SiMe)3)2]3Catalyzing intermolecular addition reaction of o-methyl phenyl isocyanate and benzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 123.98. mu.L (1.00X 10) were added-3Mole) o-methyl phenyl isocyanateThe reaction was stirred in a constant temperature bath at 40 ℃. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2136g of a target product with the yield of 83 percent. The structure of the target product is as follows:
Figure BDA0001667308870000101
nuclear magnetic data:1H NMR(400MHz,CDCl3):δ7.39-7.13(m,9H,ArH),7.02(dd,J1＝19.4,J2＝12.0Hz,2H,ArH、NH),4.15(s,2H,CH2)ppm.
example 30: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of m-methyl phenyl isocyanate and benzyl mercaptan at 40 ℃, comprising the following steps:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 128.90. mu.L (1.00X 10) were added-3Mol) of m-methyl phenyl isocyanate, and stirring the mixture in a constant temperature bath at 40 ℃ for reaction. After 30 hours, removing the protective argon gas, aerating and quenching the reaction, carrying out column chromatography by using ethyl acetate and petroleum ether (1:20) as developing agents, and spin-drying the solvent to obtain 0.2445g of a target product with the yield of 95%. The structure of the target product is as follows:
Figure BDA0001667308870000111
nuclear magnetic data:1H NMR(400MHz,CDCl3):δ7.31-6.94(m,9H,ArH),6.84(d,J＝5.7Hz,1H,NH),4.14(s,2H,CH2),2.23(s,3H,CH3)ppm.
example 31: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing an intermolecular addition reaction of p-tolylisocyanate and benzylmercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mol) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 126.09. mu.L (1.00X 10) was added-3Mol) p-methyl phenyl isocyanate, and stirring the p-methyl phenyl isocyanate in a constant temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2316g of target product with the yield of 90 percent. The structure of the target product is as follows:
Figure BDA0001667308870000112
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.31-7.05(m,8H,ArH),6.99(d,J＝8.2Hz,2H,ArH、NH),4.11(s,2H,CH2),2.20(s,3H,CH3)ppm.
example 32: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenyl fluoroisocyanate and benzyl mercaptan at 40 ℃, comprising:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 113.69. mu.L (1.00X 10) were added-3Mol) of p-fluorophenyl fluoroisocyanate, and stirring the p-fluorophenyl fluoroisocyanate in a constant temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2378g of target product with the yield of 91 percent. The structure of the target product is as follows:
Figure BDA0001667308870000113
nuclear magnetic data:1HNMR(400MHz,CDCl3):7.33-7.10(m,7H,ArH),7.07(d,J＝10.9Hz,1H,ArH),6.98-6.86(m,2H,ArH、NH),4.13(s,2H,CH2)ppm.
example 33: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of p-chlorophenyl isocyanate and benzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 127.97. mu.L (1.00X 10) were added-3Mol) p-chlorophenyl isocyanate, and the reaction is carried out in a constant temperature bath at 40 ℃. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2555g of a target product with the yield of 92 percent. The structure of the target product is as follows:
Figure BDA0001667308870000121
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.32-7.13(m,9H,ArH),7.00(s,1H,NH),4.12(s,2H,CH2)ppm.
example 34: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing an intermolecular addition reaction of p-bromophenyl isocyanate and benzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 0.1980g (1.00X 10 g) were added-3Mol) p-bromophenyl isocyanate, and stirring the p-bromophenyl isocyanate in a constant temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2964g of target product with the yield of 92 percent. The structure of the target product is as follows:
Figure BDA0001667308870000122
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.35-7.13(m,9H,ArH),7.05(s,1H,NH),4.14(s,2H,CH2)ppm.
example 35: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing an intermolecular addition reaction of p-trifluoromethylphenyl isocyanate and benzylthiol at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 142.84. mu.L (1.00X 10) were added-3Mol) of p-trifluoromethylphenyl isocyanate, and the reaction was carried out in a constant temperature bath at 40 ℃ with stirring. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2895g of a target product with the yield of 93 percent. The structure of the target product is as follows:
Figure BDA0001667308870000131
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.45(q,J＝9.0Hz,4H,ArH),7.32-7.14(m,6H,ArH、NH),4.15(s,2H,CH2)ppm.
example 36: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of p-nitrophenyl isocyanate and benzyl mercaptan at 40 ℃, comprising the following steps:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 0.1641g (1.00X 10 g) were added-3Mol) p-nitro phenyl isocyanate, and stirring the p-nitro phenyl isocyanate in a constant temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2566g of target product with 89 percent of yield. The structure of the target product is as follows:
Figure BDA0001667308870000132
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ8.13(d,J＝9.2Hz,2H,ArH),7.52(d,J＝9.2Hz,2H,ArH),7.33-7.15(m,6H,ArH、NH),4.18(s,2H,CH2)ppm.
example 37: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of p-methoxy phenyl isocyanate and benzyl mercaptan at 40 ℃, comprising the following steps:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 129.58. mu.L (1.00X 10) were added-3Mole) of p-methoxy phenyl isocyanate, and stirring the mixture in a constant temperature bath at 40 ℃ for reaction. After 30 hours, the protected argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2296g of target product with 84 percent of yield. The structure of the target product is as follows:
Figure BDA0001667308870000133
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.34-7.09(m,7H,ArH),6.91(d,J＝12.8Hz,1H,ArH),6.77(d,J＝9.0Hz,2H,ArH、NH),4.13(s,2H,CH2),3.71(s,3H,CH3)ppm.
example 38: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of 2, 6-dimethylphenyl isocyanate and benzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 139.23. mu.L (1.00X 10) were added-3Mol) 2, 6-dimethyl phenyl isocyanate, stirring and reacting in a constant temperature bath at 40 DEG C. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.1872g of target product with the yield of 69 percent. The structure of the target product is as follows:
Figure BDA0001667308870000141
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.33-6.86(m,8H,ArH),6.73(s,1H,NH),4.11(s,1H,CH2),3.98(s,1H,CH2),,2.30-1.99(m,6H,CH3)ppm.
example 39: 1 mol% of La [ N (SiMe)3)2]3A process for catalyzing the intermolecular addition reaction of 2, 6-diethylphenylisocyanate and benzylthiol at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 172.81. mu.L (1.00X 10) were added-3Mol) 2, 6-diethyl phenyl isocyanate, and stirring the mixture in a constant temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2246g of target product with the yield of 75 percent. The structure of the target product is as follows:
Figure BDA0001667308870000142
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.30-6.85(m,8H,ArH),6.54(s,1H,NH),4.14(s,1H,CH2),4.00(s,1H,CH2),2.68-2.42(m,4H,CH2),1.10(d,J＝6.0Hz,6H,CH3)ppm.
example 40: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of 2, 6-diisopropylphenyl isocyanate and benzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 1) into a reaction bottle under the protection of anhydrous oxygen-free argon gas0-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 213.75. mu.L (1.00X 10) were added-3Mol) 2, 6-diisopropyl phenyl isocyanate, and stirring the mixture in a constant temperature bath at 40 ℃ for reaction. After 30 hours, the protected argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2751g of target product with 84 percent of yield. The structure of the target product is as follows:
Figure BDA0001667308870000143
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.32-7.05(m,8H,ArH),6.54(s,1H,NH),4.14(s,1H,CH2),4.00(s,1H,CH2),3.22-3.05(m,1H,CH),3.07-2.89(m,1H,CH),1.19-1.00(m,12H,CH3)ppm.
example 41: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenyl isocyanate and o-methylbenzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]30.1382g (1.00X 10) was added-3Mol) o-methylbenzylthiol and 1mL of toluene were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) of the mixture was further added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2419g of target product with 94 percent of yield. The structure of the target product is as follows:
Figure BDA0001667308870000151
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.38-7.19(m,5H,ArH),7.12-7.00(m,4H,ArH),6.97(s,1H,NH),4.19(s,2H,CH2),2.32(s,3H,CH3)ppm.
example 42: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenyl isocyanate and p-methylbenzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3Then 135.12. mu.L (1.00X 10) was added-3Mol) p-methylbenzylthiol and 1mL of toluene were stirred at room temperature for 15min under an argon atmosphere, and 108.69. mu.L (1.00X 10) of toluene was further added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2393g of a target product with the yield of 93 percent. The structure of the target product is as follows:
Figure BDA0001667308870000152
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.32(d,J＝7.7Hz,2H,ArH),7.26-7.16(m,4H,ArH),7.06-7.01(m,3H,ArH),6.96(s,1H,NH),4.12(s,2H,CH2),2.25(s,3H,CH3)ppm.
example 43: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenyl isocyanate and p-chlorobenzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3131.99 μ L (1.00X 10) was added-3Mol) p-chlorobenzyl mercaptan and 1mL toluene were stirred at room temperature for 15min under argon atmosphere, and 108.69. mu.L (1.00X 10) was further added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2611g of target product with 94 percent of yield. The structure of the target product is as follows:
Figure BDA0001667308870000161
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.32(d,J＝7.8Hz,2H,ArH),7.29-7.15(m,6H,ArH),7.03(dd,J1＝16.0,J2＝8.6Hz,2H,ArH、NH),4.09(s,2H,CH2)ppm.
example 44: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenyl isocyanate and p-methoxybenzyl mercaptan at 40 ℃, comprising:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3139.32 μ L (1.00X 10) was added-3Mole) p-methoxybenzylthiol and 1mL of toluene were stirred at room temperature under argon atmosphere for 15min, and 108.69. mu.L (1.00X 10) was further added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2515g of target product with the yield of 92 percent. The structure of the target product is as follows:
Figure BDA0001667308870000162
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.46-7.23(m,5H,ArH),7.13(dd,J1＝19.2,J2＝11.8Hz,2H,ArH),6.35-6.20(m,2H,ArH、NH),4.26(s,2H,CH2),3.68(s,3H,CH3)ppm.
example 45: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenyl isocyanate and 2-furanmethanethiol at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3100.86 μ L (1.00X 10) was added-3Mol) 2-Furazomethane and 1mL toluene under argon atmosphere at room temperature for 15min, and 108.69 μ L (1.00X 10)-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours the guard is removedAnd (3) protecting argon gas, aerating and quenching the reaction, performing column chromatography by using ethyl acetate and petroleum ether (1:20) as developing agents, and performing spin-drying on the solvent to obtain 0.2310g of a target product with the yield of 99%. The structure of the target product is as follows:
Figure BDA0001667308870000163
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.46-7.23(m,5H,ArH),7.13(dd,J1＝19.2,J2＝11.8Hz,2H,ArH),6.35-6.20(m,2H,ArH、NH),4.26(s,2H,CH2)ppm.
example 46: 1 mol% of La [ N (SiMe)3)2]3A process for catalyzing the intermolecular addition reaction of phenyl isocyanate and cyclohexyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3122.34 μ L (1.00X 10) was added-3Mole) Cyclohexylmercaptan and 1mL of toluene were stirred at room temperature for 15min under an argon atmosphere, and 108.69. mu.L (1.00X 10) of the solution was further added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2212g of target product with 94 percent of yield. The structure of the target product is as follows:
Figure BDA0001667308870000171
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ7.41(d,J＝7.6Hz,2H,ArH),7.36-7.27(m,2H,ArH),7.08(dd,J1＝18.4,J2＝11.1Hz,2H,ArH、NH),3.59-3.50(m,1H,CH),2.08-2.00(m,2H,CH2),1.73(dd,J1＝9.4,J2＝4.0Hz,2H,CH2),1.55-1.37(m,4H,CH2),1.35-1.20(m,2H,CH2)ppm.
example 47: 1 mol% of La [ N (SiMe)3)2]3Method for catalyzing intermolecular addition reaction of phenyl isothiocyanate and triphenyl methyl mercaptan at 40 DEG C：
Adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]30.2764g (1.00X 10) was added-3Mol) Triphenyl methyl mercaptan and 1mL toluene were stirred at room temperature for 15min under argon atmosphere, and 108.69. mu.L (1.00X 10) were added-3Mol) of phenyl isocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.1424g of target product with the yield of 36 percent. The structure of the target product is as follows:
Figure BDA0001667308870000172
nuclear magnetic data:1HNMR(400MHz,DMSO-d6):δ10.32(s,1H,NH),7.37-7.10(m,19H,ArH),6.99(t,J＝7.1Hz,1H,ArH)ppm.
example 48: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenyl isothiocyanate and o-methylbenzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]30.1382g (1.00X 10) was added-3Mol) o-methylbenzylthiol and 1mL of toluene were stirred at room temperature under argon atmosphere for 15min, and 238.85. mu.L (2.00X 10) of toluene were further added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2325g of target product with the yield of 86%. The structure of the target product is as follows:
Figure BDA0001667308870000181
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ9.10(s,1H,NH),7.48-7.20(m,6H,ArH),7.20-7.05(m,3H,ArH),4.52(s,2H,CH2),2.35(s,3H,CH3)ppm.
example 49: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenylisothiocyanate and p-methylbenzylthiol at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3Then 135.12. mu.L (1.00X 10) was added-3Mol) p-methylbenzylthiol and 1mL of toluene were stirred at room temperature for 15min under an argon atmosphere, and 238.85. mu.L (2.00X 10) of toluene was further added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2406g of target product with 88 percent of yield. The structure of the target product is as follows:
Figure BDA0001667308870000182
nuclear magnetic data (. delta.8.92 (s,1H, NH),7.38(dd, J)1＝16.3,J2＝8.8Hz,4H,ArH),7.25(dd,J1＝10.2,J2＝7.7Hz,3H,ArH),7.10(d,J＝7.9Hz,2H,ArH),4.51(s,2H,CH2),2.31(s,3H,CH3)ppm.
Example 50: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenylisothiocyanate and p-chlorobenzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3131.99 μ L (1.00X 10) was added-3Mol) p-chlorobenzyl mercaptan and 1mL toluene were stirred at room temperature for 15min under argon atmosphere, and 238.85. mu.L (2.00X 10) was further added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2556g of target product with the yield of 87 percent. The structure of the target product is asThe following:
Figure BDA0001667308870000183
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ9.14(s,1H,NH),7.37(t,J＝7.6Hz,3H,ArH),7.33-7.18(m,6H,ArH),4.51(s,2H,CH2)ppm.
example 51: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenyl isothiocyanate and p-methoxybenzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3139.32 μ L (1.00X 10) was added-3Mole) p-methoxybenzylthiol and 1mL of toluene were stirred at room temperature under argon atmosphere for 15min, and 238.85. mu.L (2.00X 10) was further added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2518g of target product with the yield of 87 percent. The structure of the target product is as follows:
Figure BDA0001667308870000191
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ8.98(s,1H,NH),7.38(dd,J1＝15.6,J2＝8.0Hz,4H,ArH),7.33-7.19(m,3H,ArH),6.86-6.77(m,2H,ArH),4.50(s,2H,CH2),3.77(s,3H,CH3)ppm.
example 52: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing an intermolecular addition reaction of phenylisothiocyanate and 2-furanmethanethiol at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3100.86 μ L (1.00X 10) was added-3Mol) 2-furanmethanethiol and 1mL toluene inStirring at room temperature for 15min under argon atmosphere, and adding 238.85 μ L (2.00 × 10)-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2045g of target product with the yield of 82%. The structure of the target product is as follows:
Figure BDA0001667308870000192
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ9.09(s,1H,NH),7.51-7.26(m,6H,ArH),6.36-6.22(m,2H,ArH),4.60(s,2H,CH2)ppm.
example 53: 1 mol% of La [ N (SiMe)3)2]3A process for catalyzing an intermolecular addition reaction of phenylisothiocyanate and cyclohexylthiol at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3122.34 μ L (1.00X 10) was added-3Mole) Cyclohexylmercaptan and 1mL of toluene were stirred at room temperature for 15min under an argon atmosphere, and 238.85. mu.L (2.00X 10) of solution was further added-3Mol) phenyl isothiocyanate, and stirring the mixture in a constant-temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.1886g of target product with the yield of 75 percent. The structure of the target product is as follows:
Figure BDA0001667308870000201
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ9.11(s,1H,NH),7.39(dd,J＝14.7,7.3Hz,4H,ArH),7.28(dd,J1＝13.7,J2＝6.6Hz,1H,ArH),4.03-3.83(m,1H,CH),2.11(dd,J1＝8.5,J2＝4.7Hz,2H,CH2),1.78-1.55(m,3H,CH2),1.54-1.36(m,4H,CH2)ppm.
example 54: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenyl p-methoxyisothiocyanate and benzyl mercaptan at 40 ℃, comprising the following steps:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 276.27. mu.L (2.00X 10) were added-3Mole) of p-methoxy phenyl isothiocyanate was reacted in a constant temperature bath at 40 ℃ with stirring. After 30 hours, the protected argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2431g of target product with 84 percent of yield. The structure of the target product is as follows:
Figure BDA0001667308870000202
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ9.36(s,1H,NH),7.39-7.21(m,7H,ArH),6.93-6.84(m,2H,ArH),4.53(s,2H,CH2),3.79(s,3H,CH3)ppm.
example 55: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of phenyl paranitroisothiocyanate and benzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 0.3604g (2.00X 10 g) were added-3Mol) p-nitro phenyl isothiocyanate, and stirring the mixture in a constant temperature bath at 40 ℃ for reaction. After 30 hours, the protective argon gas is removed to aerate and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2678g of target product with 88 percent of yield. The structure of the target product is as follows:
Figure BDA0001667308870000203
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ8.86(s,1H,NH),8.24-8.11(m,2H,ArH),7.82(d,J＝9.1Hz,2H,ArH),7.38-7.22(m,5H,ArH),4.57(s,2H,CH2)ppm.
example 56: 1 mol% of La [ N (SiMe)3)2]3A method for catalyzing intermolecular addition reaction of 2, 6-dimethylphenyl isothiocyanate and benzyl mercaptan at 40 ℃:
adding 0.0062g (1.00X 10 g) into a reaction bottle under the protection of anhydrous oxygen-free argon gas-5Mole) La [ N (SiMe)3)2]3117.39 μ L (1.00X 10) was added-3Mole) benzyl mercaptan and 1mL toluene were stirred at room temperature under argon atmosphere for 15min, and 300.90. mu.L (2.00X 10) were added-3Mol) 2, 6-dimethyl phenyl isothiocyanate is stirred and reacted in a constant temperature bath at 40 ℃. After 30 hours, the protective argon gas is removed to expose and quench the reaction, column chromatography is carried out by taking ethyl acetate and petroleum ether (1:20) as developing agents, and the solvent is dried by spinning to obtain 0.2041g of target product with the yield of 71 percent. The structure of the target product is as follows:
Figure BDA0001667308870000211
nuclear magnetic data:1HNMR(400MHz,CDCl3):δ9.34(s,1H,NH),7.25-7.03(m,7H,ArH),6.98(d,J＝7.5Hz,2H,ArH),4.37(s,2H,CH2),2.18(s,6H,CH3)ppm.
the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (7)

1.一种催化异氰酸苯酯或异硫氰酸苯酯和硫醇加成反应的方法，其特征在于，包括以下步骤：1. a method for catalyzing phenyl isocyanate or phenyl isothiocyanate and thiol addition reaction, is characterized in that, comprises the following steps: 将式(1)所示的异氰酸苯酯或异硫氰酸苯酯与式(2)所示的硫醇在催化剂稀土胺化物的催化作用下，在10-75℃下反应，得到式(3)所示的硫代氨基甲酸酯类化合物，式(1)所示的异氰酸苯酯或异硫氰酸苯酯、式(2)所示的硫醇和稀土胺化物的摩尔比为10-20:10-20:0.1-1；反应路线如下：The phenyl isocyanate or phenyl isothiocyanate represented by the formula (1) and the thiol represented by the formula (2) are reacted at 10-75 ° C under the catalysis of the catalyst rare earth aminate to obtain the formula The molar ratio of the thiocarbamate compound represented by (3), the phenyl isocyanate or phenyl isothiocyanate represented by the formula (1), the thiol represented by the formula (2), and the rare earth amine compound is: 10-20:10-20:0.1-1; the reaction route is as follows:
Figure FDA0002277333410000011
Figure FDA0002277333410000011
 其中，R1和R3独立地选自氢、C1-C6烷基、卤素、C1-C6烷氧基、硝基或三氟甲基；X为氧原子或硫原子；R2为苄基、取代苄基、呋喃甲基、环己基或三苯甲基，所述取代苄基上的取代基团为C1-C6烷基、卤素或C1-C6烷氧基；wherein, R 1 and R 3 are independently selected from hydrogen, C 1 -C 6 alkyl, halogen, C 1 -C 6 alkoxy, nitro or trifluoromethyl; X is an oxygen atom or a sulfur atom; R 2 is benzyl, substituted benzyl, furanmethyl, cyclohexyl or trityl, and the substituent on said substituted benzyl is C 1 -C 6 alkyl, halogen or C 1 -C 6 alkoxy; 所述稀土胺化物的分子式为RE[N(SiMe3)2]3，其中RE选自镧、钐、钇或镱。The molecular formula of the rare earth amide is RE[N(SiMe 3 ) 2 ] 3 , wherein RE is selected from lanthanum, samarium, yttrium or ytterbium. 2.根据权利要求1所述的方法，其特征在于：所述C1-C6烷基为甲基、乙基或异丙基；所述卤素为氟、氯或溴；所述烷氧基为甲氧基、乙氧基或异丙氧基。2. The method according to claim 1, wherein: the C1 - C6 alkyl group is methyl, ethyl or isopropyl; the halogen is fluorine, chlorine or bromine; the alkoxy group is methoxy, ethoxy or isopropoxy. 3.根据权利要求1所述的方法，其特征在于：反应时间为24-36h。3. method according to claim 1 is characterized in that: the reaction time is 24-36h. 4.根据权利要求1所述的方法，其特征在于：反应在无水无氧以及含有保护气氛的密闭环境中进行。4. The method according to claim 1, wherein the reaction is carried out in an airtight environment without water and oxygen and containing a protective atmosphere. 5.根据权利要求4所述的方法，其特征在于：所述保护气氛为氩气气氛。5. The method according to claim 4, wherein the protective atmosphere is an argon atmosphere. 6.根据权利要求1所述的方法，其特征在于，反应在有机溶剂中进行，所述有机溶剂为四氢呋喃、甲苯、氯苯、三氯甲烷、二甲基亚砜和N,N-二甲基甲酰胺中的一种或几种。6. method according to claim 1 is characterized in that, reaction is carried out in organic solvent, and described organic solvent is tetrahydrofuran, toluene, chlorobenzene, chloroform, dimethyl sulfoxide and N,N-dimethyl sulfoxide One or more of the base carboxamides. 7.根据权利要求1所述的方法，其特征在于：还包括在空气中淬灭反应的步骤。7. The method of claim 1, further comprising the step of quenching the reaction in air.
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Actinide-Mediated Catalytic Addition of E-H Bonds (E = N, P, S) to Carbodiimides, Isocyanates, and Isothiocyanates;Isabell S.R.Karmel等;《Angewandte Chemie,International Edition》;20150618;第54卷(第42期);12422-12425 *
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