Method for preparing carbamate compounds from dioxazolone derivatives

Abstract

This application relates to a method for preparing carbamate compounds from dioxazolone derivatives, comprising the following steps: reacting a dioxazolone derivative with a hydroxyl-containing compound in the presence of a catalyst to prepare the carbamate compound. The catalyst includes one or more of dichlorobis(4-methylisopropylphenyl)ruthenium(II), tri(acetylacetonate)ruthenium(III), cyclooctadiene ruthenium(II) chloride, and dichloro(pentamethylcyclopentadienyl)iridium(III) dimers. This synthetic method is universally applicable to the synthesis of carbamate compounds with different group types (such as alkyl, aryl, heteroaryl, etc.), and exhibits high yields and mild reaction conditions.

Description

Technical Field

[0001] This application relates to drug synthesis, and in particular to a method for preparing carbamate compounds from dioxazolone derivatives. Background Technology

[0002] Carbamates, as a versatile structural unit, are widely used in organic synthesis, medicinal chemistry, and materials science. For example, carbamate derivatives can be used as pesticides, antiarrhythmic drugs, anti-Alzheimer's drugs, and anti-AIDS drugs. Therefore, developing simple and efficient synthetic methods for carbamate compounds is crucial. The general structural formula of carbamate compounds is shown below:

[0003] , where R 1 R 2 These are the modifying groups required for the intended use, and can include different types of groups such as substituted or unsubstituted alkyl, aryl, and heteroaryl groups.

[0004] Unfortunately, traditional synthetic methods, such as the Curtius rearrangement involving acyl azides, the reductive carbonylation of nitroaromatics, the carbonylation of amines, the reaction of alcohols with isocyanates, and the catalytic reaction of amines or azides with alcohols and carbon monoxide, all have certain limitations. For example, the reaction conditions are often harsh, and the reactions involve highly toxic reagents (phosgene and its derivatives, carbon monoxide, isocyanates, etc.). These drawbacks greatly limit their application in the synthesis of carbamate compounds. Other methods involve the CH functionalization of aryl carbamates, the reaction of cyclic carbonates with aromatic amines, and the catalytic carbonylation of amines with carbon dioxide. However, these methods are mostly used to prepare functionalized N / O-aryl or cyclic carbamate compounds, resulting in a limited range of product types.

[0005] In addition, there are methods that use dioxazolone and hydroxyl-containing compounds as substrates to prepare carbamates in the presence of a catalyst. However, these methods still have limitations in terms of product types, dependence on specific functionalized substrates (such as fluorinated alcohols), and are not universally applicable to carbamates with different group types (such as alkyl, aryl, heteroaryl, etc.). They also have poor compatibility with active functional groups (such as alkenyl, alkynyl, hydroxyl, amino, heterocyclic, etc.) and the product yield is relatively low. Summary of the Invention

[0006] Based on this, this application provides a method for preparing carbamate compounds from dioxazolone derivatives. This synthetic method is applicable to the synthesis of carbamate compounds with different group types (such as alkyl, aryl, heteroaryl, etc.), and has a high yield and mild reaction conditions.

[0007] The specific technical solution is as follows:

[0008] This application provides a method for preparing carbamate compounds from dioxazolone derivatives, comprising the following steps:

[0009] The carbamate compound is prepared by reacting a dioxazolone derivative with a hydroxyl-containing compound in the presence of a catalyst.

[0010] The catalyst comprises one or more of the following: dichlorobis(4-methylisopropylphenyl)ruthenium(II), tri(acetylacetonate)ruthenium(III), cyclooctadiene ruthenium(II) chloride, and dichloro(pentamethylcyclopentadienyl)iridium(III) dimer.

[0011] In some embodiments, the molar ratio of the catalyst, the hydroxyl-containing compound, and the dioxazolone derivative is 0.05:1:(1.1~1.5).

[0012] In some embodiments, the reaction temperature is 40°C to 80°C, and the reaction time is 10h to 20h.

[0013] In some embodiments, the reaction is carried out in the presence of a solvent, which includes one or more of 1,4-dioxane, tetrahydrofuran (THF), acetonitrile (CH3CN), N,N-dimethylformamide (DMF), dichloroethane (DCE), and toluene.

[0014] In some embodiments, a post-processing step is included after the reaction is completed. The post-processing steps include:

[0015] The reaction solution was cooled to room temperature, washed with a saturated ammonium chloride solution, and then extracted with an organic solvent.

[0016] In some embodiments, the organic solvent includes one or more of ethyl acetate and dichloromethane.

[0017] In some embodiments, the dioxazolone derivative has the following structural features:

[0018] ,

[0019] Among them, R 1 For at least one S 11 Substituted or unsubstituted C6-C15 aryl group, at least one S 11 Substituted or unsubstituted C3-C10 heteroaryl group, at least one S 12 Substituted or unsubstituted C1-C5 alkyl or C3-C10 cycloalkyl;

[0020] S 11Each independently includes: C1~C5 alkyl, halogen or C2~C5 alkenyl, S 12 Each independently includes: C6~C15 aryl or -C6~C15 aryl-C1~C5 alkoxy.

[0021] In some embodiments, the hydroxyl-containing compound has the following structural features:

[0022] ,

[0023] Among them, R 2 For S 21 Substituted or unsubstituted C6-C15 aryl group, at least one S 22 Substituted or unsubstituted C1~C5 alkyl or C2~C10 alkenyl;

[0024] S 21 Each independently includes: C1~C5 alkoxy, C1~C5 alkyl, -C1~C5 alkyl-C6~C15 aryl-OH, -C(O)O-C1~C3 alkyl or cyano, S 22 Each independently includes: C6~C15 aryl or C3~C10 heteroaryl.

[0025] Accordingly, the carbamate compounds have the following structural features:

[0026] .

[0027] In some implementations, R 1 It has one or more of the following characteristics:

[0028] (1) C6~C15 aryl groups include C6~C10 aryl groups, and may optionally include phenyl or naphthyl groups;

[0029] (2) C3~C10 heteroaryl groups include C3~C8 heteroaryl groups, which may include thiophene, furanyl or indole;

[0030] (3) C1~C5 alkyl groups include C1~C3 alkyl groups;

[0031] (4) C3~C10 cycloalkyl groups include C4~C6 cycloalkyl groups.

[0032] In some embodiments, the dioxazolone derivative includes 3-(4-tolyl)-1,4,2-dioxazol-5-one, 3-(4-chlorophenyl)-1,4,2-dioxazol-5-one, 3-(4-vinylphenyl)-1,4,2-dioxazol-5-one, 3-(2-naphthyl)-1,4,2-dioxazol-5-one, 3-(2-furan)-1,4,2-dioxazol-5-one, and 3-(2-thiophene)-1,4,2-dioxazol-5-one. One or more of the following: 3-(4-vinylphenyl)-1,4,2-dioxazol-5-one, 3-benzyl-1,4,2-dioxazol-5-one, 3-methyl-1,4,2-dioxazol-5-one, 3-cyclopentyl-1,4,2-dioxazol-5-one, (S)-3-(1-(6-methoxynaphthyl-2-yl)ethyl)-1,4,2-dioxazol-5-one and 3-(1-methyl-1H-indol-3-yl)-1,4,2-dioxazol-5-one.

[0033] In some implementations, R 2 It has one or more of the following characteristics:

[0034] (1) C6~15 aryl groups include C6~10 aryl groups, optionally including phenyl or naphthyl groups;

[0035] (2) C1~C5 alkyl groups include C1~C3 alkyl groups;

[0036] (3) C3~10 heteroaryl groups include C3~C5 heteroaryl groups, which may include thiophene, furanyl or pyridinyl.

[0037] In some embodiments, the hydroxyl-containing compound includes one or more of phenol, 2-methoxyphenol, 2,2-bis(4′-hydroxyphenyl)propane, methyl 3-hydroxybenzoate, 3-hydroxybenzonitrile, 4-methylphenol, 1-naphthol, 2-naphthol, phenethyl alcohol, furfuryl alcohol, thiophene-3-ethanol, 4-pyridinemethanol, and nerol.

[0038] The above-mentioned method for preparing carbamate compounds uses dioxazolone derivatives and hydroxyl-containing compounds as reactants, and employs a specific catalyst for catalysis. This method is adaptable to different types of reaction substrates and is compatible with major active functional groups (such as cyano, thiophene, pyridine, indole, etc.). At the same time, the reaction has high selectivity and can effectively improve the yield of different types of products. It has broad application prospects in the fields of pesticides or pharmaceuticals that use carbamate compounds as intermediates or products.

[0039] In addition, the above synthesis method has the following advantages:

[0040] (1) The raw materials for the reaction are stable and readily available, the reaction conditions are simple and mild, the operation is simple, and there is no need to use expensive or dangerous chemicals or harsh reaction conditions, which is conducive to industrial production;

[0041] (2) Few by-products, easy product separation, no need for complicated purification steps, and simple post-processing. Detailed Implementation

[0042] The method for preparing carbamate compounds from dioxazolone derivatives according to this application is further described in detail below with reference to specific embodiments. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0043] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0044] In this article, "one or more" refers to any one, two or more of the listed items.

[0045] In this application, terms such as "first aspect," "second aspect," "third aspect," and "fourth aspect" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, terms such as "first," "second," "third," and "fourth" serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0046] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0047] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0048] Unless otherwise specified, the percentage content mentioned in this application refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.

[0049] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0050] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows for temperature fluctuations within the precision range controlled by the instrument.

[0051] In this application, room temperature generally refers to 4℃~30℃, and preferably 20±5℃.

[0052] In this document, the term "aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl; for polycyclic compounds, at least one must be an aromatic ring system. For example, "C6-C15 aryl" refers to an aryl group containing 6 to 15 carbon atoms, and each occurrence can be independently C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, or C15 aryl. Suitable examples include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene, dinaphthalene, triphenylene oxide, and their derivatives.

[0053] In this article, the term "heteroaryl" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, an O atom, an S atom, etc. For example, "C3~C10 heteroaryl" refers to a heteroaryl group containing 3 to 10 carbon atoms, and each occurrence can be independently C3 heteroaryl, C4 heteroaryl, C5 heteroaryl, C6 heteroaryl, C7 heteroaryl, C8 heteroaryl, C9 heteroaryl, or C10 heteroaryl. Suitable examples include, but are not limited to: furanyl, benzofuranyl, thiophenyl, benzothiophenyl, pyrroleyl, pyrazolyl, triazolyl, imidazoyl, oxazolyl, oxadiazolyl, thiazoyl, tetrazolyl, indolyl, carbazoyl, pyrroloimidazoyl, pyrrolopyrroleyl, thiophenolopyrroleyl, thiophenolothiophenyl, furanolopyrroleyl, furanolofuranyl, thiophenolofuranyl, benzoisooxazolyl, benzoisothiazoyl, benzoimidazoyl, pyridinyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, o-diazanaphthyl, quinoxalinyl, phenanthridine, primidinyl, quinazolinyl, and quinazolinoneyl.

[0054] In this document, the term "alkyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. Phrases containing this term, such as "C1-C5 alkyl," refer to alkyl groups containing 1 to 5 carbon atoms, and each occurrence can be independently referred to as C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, and C5 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t- Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3).

[0055] In this document, the term "cycloalkyl" refers to a non-aromatic hydrocarbon containing a ring of carbon atoms, which can be monocycloalkyl, spirocycloalkyl, or bridged cycloalkyl. Phrases containing this term, such as "C3-C10 cycloalkyl," refer to cycloalkyl compounds containing 3 to 10 carbon atoms, and each occurrence can independently be C3, C4, C5, C6, C7, C8, C9, or C10 cycloalkyl. Suitable examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Additionally, "cycloalkyl" may also contain one or more double bonds; representative examples of cycloalkyl compounds containing double bonds include cyclopentenyl, cyclohexenyl, cyclohexadienyl, and cyclobutadienyl.

[0056] In this article, the term "halogen" or "halogen group" refers to F, Cl, Br, or I.

[0057] In this document, the term "alkenyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a hydrocarbon containing at least one unsaturated carbon-carbon sp2 double bond, i.e., a carbon atom, secondary carbon atom, tertiary carbon atom, or cyclic carbon atom. Phrases containing this term, such as "C2-C5 alkenyl," refer to alkenyl groups containing 2 to 5 carbon atoms, and each occurrence can be independently C2-alkenyl, C3-alkenyl, C4-alkenyl, or C5-alkenyl. Suitable examples include, but are not limited to, vinyl (-CH=CH2), allyl (-CH2CH=CH2), cyclopentenyl (-C5H7), and 5-hexenyl (-CH2CH2CH2CH2CH=CH2).

[0058] In this document, the term "alkoxy" refers to a group with the structure -O-alkyl, i.e., an alkyl group as defined above connected to an adjacent group via an oxygen atom. Phrases containing this term, such as "C1-C5 alkoxy," refer to alkyl moieties containing 1-5 carbon atoms, and each occurrence can be independently C1 alkoxy, C2 alkoxy, C3 alkoxy, C4 alkoxy, or C5 alkoxy. Suitable examples include, but are not limited to: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), and tert-butoxy (-OC(CH3)3 or -OtBu).

[0059] Some embodiments of this application provide a method for preparing carbamate compounds from dioxazolone derivatives, comprising the following steps:

[0060] The carbamate compound is prepared by reacting a dioxazolone derivative with a hydroxyl-containing compound in the presence of a catalyst; the catalyst includes one or more of dichlorobis(4-methylisopropylphenyl)ruthenium(II), tri(acetylacetonate)ruthenium(III), cyclooctadiene ruthenium(II) chloride, and dichloro(pentamethylcyclopentadienyl)iridium(III) dimer.

[0061] In some embodiments, the molar ratio of the catalyst, the hydroxyl-containing compound, and the dioxazolone derivative is 0.05:1:(1.1~1.5). Specifically, this molar ratio includes, but is not limited to, 0.05:1:1.1, 0.05:1:1.2, 0.05:1:1.3, 0.05:1:1.4, 0.05:1:1.5, or a range between the two.

[0062] In some embodiments, the reaction temperature is 40°C to 80°C, and the reaction time is 10h to 20h. Specifically, the reaction temperature includes, but is not limited to: 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, or a range between the two; the reaction time includes, but is not limited to: 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, or a range between the two. Further, the reaction temperature is 60°C to 80°C, and the reaction time is 14h to 18h.

[0063] Without limitation, the reaction is carried out in the presence of a solvent. In some embodiments, the solvent includes one or more of 1,4-dioxane, tetrahydrofuran (THF), acetonitrile (CH3CN), N,N-dimethylformamide (DMF), dichloroethane (DCE), and toluene.

[0064] Without limitation, the reaction is carried out under an inert atmosphere, such as nitrogen.

[0065] In some embodiments, a post-processing step is included after the reaction is completed. The post-processing steps include:

[0066] The reaction solution was cooled to room temperature, washed with a saturated ammonium chloride solution, and then extracted with an organic solvent.

[0067] Without limitation, the extraction process also includes steps such as drying the extract, vacuum distillation, and column chromatography separation.

[0068] In some embodiments, the organic solvent includes one or more of ethyl acetate and dichloromethane.

[0069] In some embodiments, the dioxazolone derivative has the following structural features:

[0070] ,

[0071] Among them, R 1 For at least one S 11 Substituted or unsubstituted C6-C15 aryl group, at least one S 11 Substituted or unsubstituted C3-C10 heteroaryl group, at least one S 12 Substituted or unsubstituted C1-C5 alkyl or C3-C10 cycloalkyl;

[0072] S 11 Each independently includes: C1~C5 alkyl, halogen or C2~C5 alkenyl, S 12 Each independently includes: C6~C15 aryl or -C6~C15 aryl-C1~C5 alkoxy.

[0073] In some embodiments, the hydroxyl-containing compound has the following structural features:

[0074] ,

[0075] Among them, R 2 For S 21 Substituted or unsubstituted C6-C15 aryl group, at least one S 22 Substituted or unsubstituted C1~C5 alkyl or C2~C10 alkenyl;

[0076] S 21 Each independently includes: C1~C5 alkoxy, C1~C5 alkyl, -C1~C5 alkyl-C6~C15 aryl-OH, -C(O)O-C1~C3 alkyl or cyano, S 22 Each independently includes: C6~C15 aryl or C3~C10 heteroaryl.

[0077] Accordingly, the carbamate compounds have the following structural features:

[0078] .

[0079] In some embodiments, in the dioxazolone derivative, R 1 It has one or more of the following characteristics:

[0080] (1) C6~C15 aryl groups include C6~C10 aryl groups, and may optionally include phenyl or naphthyl groups;

[0081] (2) C3~C10 heteroaryl groups include C3~C8 heteroaryl groups, which may include thiophene, furanyl or indole;

[0082] (3) C1~C5 alkyl groups include C1~C3 alkyl groups;

[0083] (4) C3~C10 cycloalkyl groups include C4~C6 cycloalkyl groups.

[0084] Without limitation, the dioxazolone derivatives include 3-(4-tolyl)-1,4,2-dioxazol-5-one, 3-(4-chlorophenyl)-1,4,2-dioxazol-5-one, 3-(4-vinylphenyl)-1,4,2-dioxazol-5-one, 3-(2-naphthyl)-1,4,2-dioxazol-5-one, 3-(2-furan)-1,4,2-dioxazol-5-one, 3-(2-thiophene)-1,4,2-dioxazol-5-one, 3 One or more of the following: (4-vinylphenyl)-1,4,2-dioxazol-5-one, 3-benzyl-1,4,2-dioxazol-5-one, 3-methyl-1,4,2-dioxazol-5-one, 3-cyclopentyl-1,4,2-dioxazol-5-one, (S)-3-(1-(6-methoxynaphthyl-2-yl)ethyl)-1,4,2-dioxazol-5-one and 3-(1-methyl-1H-indol-3-yl)-1,4,2-dioxazol-5-one.

[0085] In some embodiments, in the hydroxyl-containing compound, R 2 It has one or more of the following characteristics:

[0086] (1) C6~15 aryl groups include C6~10 aryl groups, optionally including phenyl or naphthyl groups;

[0087] (2) C1~C5 alkyl groups include C1~C3 alkyl groups;

[0088] (3) C3~10 heteroaryl groups include C3~C5 heteroaryl groups, which may include thiophene, furanyl or pyridinyl.

[0089] Without limitation, the hydroxyl-containing compound includes one or more of phenol, 2-methoxyphenol, 2,2-bis(4′-hydroxyphenyl)propane, methyl 3-hydroxybenzoate, 3-hydroxybenzonitrile, 4-methylphenol, 1-naphthol, 2-naphthol, phenethyl alcohol, furfuryl alcohol, thiophene-3-ethanol, 4-pyridinemethanol, and nerol.

[0090] For experimental parameters not specified in the following specific embodiments, please refer to the guidelines given in this application document first, or refer to experimental manuals or other experimental methods known in the art, or refer to the experimental conditions recommended by the manufacturer.

[0091] The raw materials and reagents involved in the following specific embodiments can be obtained commercially or prepared by those skilled in the art using known methods.

[0092] The synthetic reaction formulas of the carbamate compounds involved in the examples are shown below:

[0093] ,

[0094] Among them, R1 R 2 The definition is as described above.

[0095] Example 1

[0096] This embodiment provides a carbamate compound: phenyl(4-tolyl)carbamate, the specific structure of which is shown below:

[0097] .

[0098] This embodiment provides a method for preparing phenyl(4-tolyl)carbamate, including:

[0099] 0.1 mmol phenol, 0.15 mmol 3-(4-tolyl)-1,4,2-dioxazol-5-one, 0.005 mmol dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 92% and a purity greater than 97%.

[0100] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.40-7.35 (m, 2H), 7.31 (d, J = 7.4 Hz, 2H), 7.25-7.20 (m, 1H), 7.20-7.16 (m, 2H), 7.11 (d, J = 8.3 Hz, 2H), 7.02 (s, 1H), 2.31 (s, 3H).

[0101] Example 2

[0102] This embodiment provides a carbamate compound: phenyl(4-chlorophenyl)carbamate, the specific structure of which is shown below:

[0103] .

[0104] This embodiment provides a method for preparing phenyl (4-chlorophenyl)carbamate, including:

[0105] 0.1 mmol phenol, 0.15 mmol 3-(4-chlorophenyl)-1,4,2-dioxazol-5-one, 0.005 mmol ruthenium(II) dichloride of cyclooctadiene, and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 94% and a purity greater than 96%.

[0106] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.42-7.35 (m, 4H), 7.29-7.23 (m, 3H), 7.20-7.16 (m, 2H), 7.08 (s, 1H).

[0107] Example 3

[0108] This embodiment provides a carbamate compound: phenyl(4-vinylphenyl)carbamate, the specific structure of which is shown below:

[0109] .

[0110] This embodiment provides a method for preparing phenyl (4-vinylphenyl)carbamate, including:

[0111] 0.1 mmol phenol, 0.15 mmol 3-(4-vinylphenyl)-1,4,2-dioxazol-5-one, 0.005 mmol dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 97% and a purity greater than 96%.

[0112] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.43-7.32 (m, 6H), 7.25 (t, J = 7.4 Hz, 1H), 7.22-7.12 (m, 3H), 6.68 (dd, J = 17.6, 10.9 Hz, 1H), 5.69 (d, J = 17.6 Hz, 1H), 5.21 (d, J =10.9 Hz, 1H).

[0113] Example 4

[0114] This embodiment provides a carbamate compound: phenyl(2-naphthyl)carbamate, the specific structure of which is shown below:

[0115] .

[0116] This embodiment provides a method for preparing phenyl(2-naphthyl)carbamate, including:

[0117] 0.1 mmol phenol, 0.15 mmol 3-(2-naphthyl)-1,4,2-dioxazol-5-one, 0.005 mmol dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 50 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 95% and a purity greater than 96%.

[0118] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 8.06 (s, 1H), 7.85-7.75 (m, 3H), 7.50-7.38 (m, 5H), 7.31-7.21 (m, 3H), 7.18 (s, 1H).

[0119] Example 5

[0120] This embodiment provides a carbamate compound: phenyl(2-furan)carbamate, the specific structure of which is shown below:

[0121] .

[0122] This embodiment provides a method for preparing phenyl(2-furan)carbamate, including:

[0123] 0.1 mmol phenol, 0.15 mmol 3-(2-furan)-1,4,2-dioxazol-5-one, 0.005 mmol dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 53% and a purity greater than 96%.

[0124] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.42-7.36 (m, 2H), 7.27-7.22 (m, 1H), 7.22-7.06 (m, 4H), 6.39 (dd,J = 3.2, 2.0 Hz, 1H), 6.18 (s, 1H).

[0125] Example 6

[0126] This embodiment provides a carbamate compound: phenyl(2-thiophene) carbamate, the specific structure of which is shown below:

[0127] .

[0128] This embodiment provides a method for preparing phenyl(2-thiophene)carbamate, including:

[0129] 0.1 mmol phenol, 0.12 mmol 3-(2-thiophene)-1,4,2-dioxazol-5-one, 0.005 mmol dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 88% and a purity greater than 97%.

[0130] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.55 (s, 1H), 7.42-7.35 (m, 2H), 7.26-7.23 (m, 1H), 7.22-7.17 (m,2H), 6.90 (d, J = 4.9 Hz, 1H), 6.86-6.83 (m, 1H), 6.68 (s, 1H).

[0131] Example 7

[0132] This embodiment provides a carbamate compound: phenylbenzyl carbamate, the specific structure of which is shown below:

[0133] .

[0134] This embodiment provides a method for preparing phenyl benzyl carbamate, including:

[0135] 0.1 mmol phenol, 0.15 mmol 3-benzyl-1,4,2-dioxazol-5-one, 0.005 mmol ruthenium(III) tris(acetylacetonate), and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 20 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 61% and a purity greater than 96%.

[0136] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.40-7.34 (m, 6H), 7.34-7.29 (m, 1H), 7.21 (t, J = 7.4 Hz, 1H), 7.16 (d, J = 7.7 Hz, 2H), 5.39 (s, 1H), 4.46 (d, J = 6.0 Hz, 2H).

[0137] Example 8

[0138] This embodiment provides a carbamate compound: phenylmethyl carbamate, the specific structure of which is shown below:

[0139] .

[0140] This embodiment provides a method for preparing phenyl methyl carbamate, including:

[0141] 0.1 mmol phenol, 0.15 mmol 3-methyl-1,4,2-dioxazol-5-one, 0.005 mmol dichloro(pentamethylcyclopentadienyl)iridium(III) dimer, and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 80 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 77% and a purity greater than 96%.

[0142] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1H NMR (600 MHz, CDCl3): δ 7.35 (t, J = 7.9 Hz, 2H), 7.19 (t, J = 7.4 Hz, 1H), 7.12 (d, J =7.9 Hz, 2H), 5.06 (s, 1H), 2.87 (d, J = 4.1 Hz, 3H).

[0143] Example 9

[0144] This embodiment provides a carbamate compound: phenylcyclopentyl carbamate, the specific structure of which is shown below:

[0145] .

[0146] This embodiment provides a method for preparing phenylcyclopentylcarbamate, including:

[0147] 0.1 mmol phenol, 0.15 mmol 3-cyclopentyl-1,4,2-dioxazol-5-one, 0.005 mmol dichloro(pentamethylcyclopentadienyl)iridium(III) dimer, and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 80 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 65% and a purity greater than 96%.

[0148] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.35 (t, J = 7.8 Hz, 2H), 7.18 (t, J = 7.4 Hz, 1H), 7.12 (d, J =7.9 Hz, 2H), 4.96 (s, 1H), 4.11-4.01 (m, 1H), 2.07-1.98 (m, 2H), 1.78-1.62(m, 4H), 1.53-1.47 (m, 2H).

[0149] Example 10

[0150] This embodiment provides a carbamate compound: 2-methoxyphenyl(4-tolyl)carbamate, the specific structure of which is shown below:

[0151] .

[0152] This embodiment provides a method for preparing 2-methoxyphenyl (4-tolyl) carbamate, including:

[0153] 0.1 mmol of 2-methoxyphenol, 0.15 mmol of 3-(4-tolyl)-1,4,2-dioxazol-5-one, 0.005 mmol of dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL of CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 10 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 96% and a purity greater than 96%.

[0154] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.33 (d, J = 7.9 Hz, 2H), 7.22 (t, J = 7.2 Hz, 1H), 7.17 (d, J =7.8 Hz, 1H), 7.13 (d, J = 8.2 Hz, 2H), 7.06 (s, 1H), 7.00-6.95 (m, 2H), 3.85(s, 3H), 2.32 (s, 3H).

[0155] Example 11

[0156] This embodiment provides a carbamate compound: 4-(2-(4-hydroxyphenyl)isopropyl)phenyl(4-tolyl)carbamate, the specific structure of which is shown below:

[0157] .

[0158] This embodiment provides a method for preparing 4-(2-(4-hydroxyphenyl)isopropyl)phenyl(4-tolyl)carbamate, including:

[0159] 0.1 mmol of 2,2-bis(4′-hydroxyphenyl)propane, 0.15 mmol of 3-(4-tolyl)-1,4,2-dioxazol-5-one, 0.005 mmol of dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL of CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 60%.

[0160] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.32 (d, J = 6.0 Hz, 2H), 7.22 (d, J = 7.7 Hz, 2H), 7.13 (d, J =8.1 Hz, 2H), 7.07 (t, J = 9.2 Hz, 4H), 6.90 (s, 1H), 6.71 (d, J = 8.3 Hz,2H), 5.03 (s, 1H), 2.32 (s, 3H), 1.64 (s, 6H).

[0161] Example 12

[0162] This embodiment provides a carbamate compound: 1-naphthyl(4-tolyl)carbamate, the specific structure of which is shown below:

[0163] .

[0164] This embodiment provides a method for preparing 1-naphthyl(4-tolyl)carbamate, including:

[0165] Add 0.1 mmol of 1-naphthol, 0.15 mmol of 3-(4-tolyl)-1,4,2-dioxazol-5-one, and 0.005 mmol of dichlorobis(4-methylisopropylphenyl)ruthenium(II) to the reactor. , 1.0 mL of 1,4-dioxane solvent. Under a nitrogen atmosphere, the mixture was heated to 60 °C and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 43% and a purity greater than 96%.

[0166] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 8.01 (s, 1H), 7.89 (dd, J = 6.2, 3.2 Hz, 1H), 7.76 (d, J = 8.2 Hz, 1H), 7.55-7.44 (m, 3H), 7.37 (t, J = 6.4 Hz, 3H), 7.22 (s, 1H), 7.15 (d, J =8.0 Hz, 2H), 2.33 (s, 3H).

[0167] Example 13

[0168] This embodiment provides a carbamate compound: 2-naphthyl(4-tolyl) carbamate, the specific structure of which is shown below:

[0169] .

[0170] This embodiment provides a method for preparing 2-naphthyl(4-tolyl)carbamate, including:

[0171] 0.1 mmol of 2-naphthol, 0.15 mmol of 3-(4-tolyl)-1,4,2-dioxazol-5-one, 0.005 mmol of dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL of CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 85% and a purity greater than 96%.

[0172] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.89-7.79 (m, 3H), 7.66 (s, 1H), 7.52-7.44 (m, 2H), 7.38-7.31 (m,3H), 7.15 (d, J = 7.9 Hz, 2H), 6.97 (s, 1H), 2.33 (s, 3H).

[0173] Example 14

[0174] This embodiment provides a carbamate compound: phenethyl (4-tolyl) carbamate, the specific structure of which is shown below:

[0175] .

[0176] This embodiment provides a method for preparing phenethyl (4-tolyl) carbamate, including:

[0177] 0.1 mmol phenylethanol, 0.15 mmol 3-(4-tolyl)-1,4,2-dioxazol-5-one, 0.005 mmol dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 90% and a purity greater than 96%.

[0178] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.36-7.31 (m, 2H), 7.30-7.20 (m, 5H), 7.11 (d, J = 8.2 Hz, 2H), 6.60 (s, 1H), 4.40 (t, J = 7.0 Hz, 2H), 3.00 (t, J = 7.0 Hz, 2H), 2.32 (s,3H).

[0179] Example 15

[0180] This embodiment provides a carbamate compound: 2-(3-thiophene)ethyl(4-tolyl)carbamate, the specific structure of which is shown below:

[0181] .

[0182] This embodiment provides a method for preparing 2-(3-thiophene)ethyl(4-tolyl)carbamate, including:

[0183] 0.1 mmol thiophene-3-ethanol, 0.15 mmol 3-(4-tolyl)-1,4,2-dioxazol-5-one, 0.005 mmol dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 83% and a purity greater than 96%.

[0184] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.26 (s, 2H), 7.18 (dd, J = 5.1, 1.1 Hz, 1H), 7.11 (d, J = 8.3 Hz, 2H), 6.96 (dd, J = 5.1, 3.4 Hz, 1H), 6.89 (d, J = 3.3 Hz, 1H), 6.66 (s, 1H), 4.40 (t, J = 6.7 Hz, 2H), 3.21 (t, J = 6.7 Hz, 2H), 2.31 (s, 3H).

[0185] Example 16

[0186] This embodiment provides a carbamate compound: 3-cyanophenyl-p-tolyl carbamate, the specific structure of which is shown below:

[0187] .

[0188] This embodiment provides a method for preparing 3-cyanophenyl-p-tolylcarbamate, including:

[0189] 0.1 mmol of 3-hydroxybenzonitrile, 0.15 mmol of 3-(4-tolyl)-1,4,2-dioxazol-5-one, 0.005 mmol of dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL of CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 18 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 95% and a purity greater than 96%.

[0190] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.53–7.43 (m, 4H), 7.32 (d, J = 7.7 Hz, 2H), 7.15 (d, J = 8.2 Hz, 2H), 7.11 (s, 1H), 2.33 (s, 3H).

[0191] Example 17

[0192] This embodiment provides a carbamate compound: phenyl(1-methyl-1H-indol-3-yl)carbamate, the specific structure of which is shown below:

[0193] .

[0194] This embodiment provides a method for preparing phenyl (1-methyl-1H-indole-3-yl)carbamate, including:

[0195] 0.1 mmol of phenol, 0.15 mmol of 3-(1-methyl-1H-indol-3-yl)-1,4,2-dioxazol-5-one, 0.005 mmol of dichloro(pentamethylcyclopentadienyl)iridium(III) dimer, and 1.0 mL of CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 20 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 63% and a purity greater than 96%. No complex purification steps were required, the operation was simple, and it was easy to scale up.

[0196] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.49 (d, J = 7.9 Hz, 1H), 7.39–7.32 (m, 3H), 7.28–7.17 (m, 5H), 7.14–7.07 (m, 2H), 3.64 (s, 3H).

[0197] Example 18

[0198] This embodiment provides a carbamate compound: phenyl(S)-(1-(6-methoxynaphth-2-yl)ethyl)carbamate, the specific structure of which is shown below:

[0199] .

[0200] This embodiment provides a method for preparing phenyl(S)-(1-(6-methoxynaphthyl-2-yl)ethyl)carbamate, including:

[0201] 0.1 mmol of 3-hydroxybenzonitrile, 0.15 mmol of (S)-3-(1-(6-methoxynaphthyl-2-yl)ethyl)-1,4,2-dioxazol-5-one, 0.005 mmol of dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL of CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 88% and a purity greater than 96%.

[0202] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1H NMR (600 MHz, CDCl3): δ 7.78–7.70 (m, 3H), 7.46 (d, J = 8.3 Hz, 1H), 7.34 (t, J = 7.5 Hz, 2H), 7.20–7.09 (m, 5H), 5.40–5.33 (m, 1H), 5.10–5.01 (m, 1H), 3.93 (s, 3H), 1.65 (d, J = 6.8 Hz, 3H).

[0203] Example 19

[0204] This embodiment provides a carbamate compound: methyl 3-(p-toluenecarbamoyl)oxy)benzoate, the specific structure of which is shown below:

[0205] .

[0206] This embodiment provides a method for preparing methyl 3-(p-toluenecarbamoyl)oxy)benzoate, including:

[0207] 0.1 mmol of methyl 3-hydroxybenzoate, 0.15 mmol of 3-(4-tolyl)-1,4,2-dioxazol-5-one, 0.005 mmol of dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL of CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 16 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 87% and a purity greater than 96%.

[0208] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.92 (dt, J = 7.7, 1.3 Hz, 1H), 7.88–7.84 (m, 1H), 7.46 (t, J = 7.9Hz, 1H), 7.40 (ddd, J = 8.1, 2.4, 1.1 Hz, 1H), 7.33 (d, J = 7.6 Hz, 2H), 7.15 (d, J = 8.2 Hz, 2H), 6.96 (s, 1H), 3.92 (s, 3H), 2.33 (s, 3H).

[0209] Example 20

[0210] This embodiment provides a carbamate compound: (Z)-3,7-dimethyl-2,6-dien-1-yl-p-tolyl carbamate, the specific structure of which is shown below:

[0211] .

[0212] This embodiment provides a method for preparing (Z)-3,7-dimethyl-2,6-dien-1-yl-p-tolyl carbamate, comprising:

[0213] 0.1 mmol nerol, 0.15 mmol 3-(4-tolyl)-1,4,2-dioxazol-5-one, 0.005 mmol dichlorobis(4-methylisopropylphenyl)ruthenium(II), and 1.0 mL CH3CN solvent were added to the reactor. The mixture was heated to 60 °C under a nitrogen atmosphere and stirred continuously for 10 h. The reaction was then stopped, cooled to room temperature, washed with saturated ammonium chloride solution, extracted with ethyl acetate, dried, and the solvent was removed by vacuum distillation. The crude product was separated by rapid column chromatography to obtain the target product, with a yield of 70% and a purity greater than 96%.

[0214] The specific 1H NMR spectrum information of the target product in this embodiment is shown below: 1 H NMR (600 MHz, CDCl3): δ 7.25 (d, J = 8.5 Hz, 2H), 7.10 (d, J = 8.3 Hz, 2H), 6.57 (s, 1H), 5.41 (t, J = 7.2 Hz, 1H), 5.11 (t, J = 7.0 Hz, 1H), 4.65 (d, J = 7.2 Hz, 2H), 2.30 (s, 3H), 2.17–2.13 (m, 2H), 2.10 (q, J = 7.3 Hz, 2H), 1.78 (s, 3H), 1.69 (s, 3H), 1.61 (s, 3H).

[0215] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0216] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A method for preparing carbamate compounds from dioxazolone derivatives, characterized in that, Includes the following steps: The carbamate compound is prepared by reacting a dioxazolone derivative with a hydroxyl-containing compound in the presence of a catalyst. The catalyst comprises one or more of the following: dichlorobis(4-methylisopropylphenyl)ruthenium(II), tri(acetylacetonate)ruthenium(III), cyclooctadiene ruthenium(II) chloride, and dichloro(pentamethylcyclopentadienyl)iridium(III) dimer.

2. The method for preparing carbamate compounds from dioxazolone derivatives according to claim 1, characterized in that, The molar ratio of the catalyst, the hydroxyl-containing compound, and the dioxazolone derivative is 0.05:1:(1.1~1.5).

3. The method for preparing carbamate compounds from dioxazolone derivatives according to claim 1, characterized in that, The reaction temperature is 40℃~80℃, and the reaction time is 10h~20h.

4. The method for preparing carbamate compounds from dioxazolone derivatives according to claim 1, characterized in that, The reaction is carried out in the presence of a solvent, which includes one or more of 1,4-dioxane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, dichloroethane, and toluene.

5. The method for preparing carbamate compounds from dioxazolone derivatives according to claim 1, characterized in that, After the reaction is complete, post-processing is also included, and the post-processing steps include: The reaction solution was cooled to room temperature, washed with a saturated ammonium chloride solution, and then extracted with an organic solvent. Optionally, the organic solvent includes one or more of ethyl acetate and dichloromethane.

6. The method for preparing carbamate compounds from dioxazolone derivatives according to any one of claims 1 to 5, characterized in that, The dioxazolone derivative has the following structural features: ， Among them, R 1 For at least one S 11 Substituted or unsubstituted C6-C15 aryl group, at least one S 11 Substituted or unsubstituted C3-C10 heteroaryl group, at least one S 12 Substituted or unsubstituted C1-C5 alkyl or C3-C10 cycloalkyl; S 11 Each independently includes: C1~C5 alkyl, halogen or C2~C5 alkenyl, S 12 Each independently includes: C6~C15 aryl or -C6~C15 aryl-C1~C5 alkoxy; The hydroxyl-containing compound has the following structural features: ， Among them, R 2 For S 21 Substituted or unsubstituted C6-C15 aryl group, at least one S 22 Substituted or unsubstituted C1~C5 alkyl or C2~C10 alkenyl; S 21 Each independently includes: C1~C5 alkoxy, C1~C5 alkyl, -C1~C5 alkyl-C6~C15 aryl-OH, -C(O)O-C1~C3 alkyl or cyano, S 22 Each independently includes: C6~C15 aryl or C3~C10 heteroaryl; The carbamate compounds have the following structural features: 。 7. The method for preparing carbamate compounds from dioxazolone derivatives according to claim 6, characterized in that, R 1 It has one or more of the following characteristics: (1) C6~C15 aryl groups include C6~C10 aryl groups, and may optionally include phenyl or naphthyl groups; (2) C3~C10 heteroaryl groups include C3~C8 heteroaryl groups, which may include thiophene, furanyl or indole; (3) C1~C5 alkyl groups include C1~C3 alkyl groups; (4) C3~C10 cycloalkyl groups include C4~C6 cycloalkyl groups.

8. The method for preparing carbamate compounds from dioxazolone derivatives according to claim 7, characterized in that, The dioxazolone derivatives include 3-(4-tolyl)-1,4,2-dioxazol-5-one, 3-(4-chlorophenyl)-1,4,2-dioxazol-5-one, 3-(4-vinylphenyl)-1,4,2-dioxazol-5-one, 3-(2-naphthyl)-1,4,2-dioxazol-5-one, 3-(2-furan)-1,4,2-dioxazol-5-one, 3-(2-thiophene)-1,4,2-dioxazol-5-one, 3-(4-) ... One or more of the following: (-vinylphenyl)-1,4,2-dioxazol-5-one, 3-benzyl-1,4,2-dioxazol-5-one, 3-methyl-1,4,2-dioxazol-5-one, 3-cyclopentyl-1,4,2-dioxazol-5-one, (S)-3-(1-(6-methoxynaphthyl-2-yl)ethyl)-1,4,2-dioxazol-5-one and 3-(1-methyl-1H-indol-3-yl)-1,4,2-dioxazol-5-one.

9. The method for preparing carbamate compounds from dioxazolone derivatives according to claim 6, characterized in that, R 2 It has one or more of the following characteristics: (1) C6~15 aryl groups include C6~10 aryl groups, optionally including phenyl or naphthyl groups; (2) C1~C5 alkyl groups include C1~C3 alkyl groups; (3) C3~10 heteroaryl groups include C3~C5 heteroaryl groups, which may include thiophene, furanyl or pyridinyl.

10. The method for preparing carbamate compounds from dioxazolone derivatives according to claim 9, characterized in that, The hydroxyl-containing compounds include one or more of phenol, 2-methoxyphenol, 2,2-bis(4′-hydroxyphenyl)propane, methyl 3-hydroxybenzoate, 3-hydroxybenzonitrile, 4-methylphenol, 1-naphthol, 2-naphthol, phenethyl alcohol, furfuryl alcohol, thiophene-3-ethanol, 4-pyridinemethanol, and nerol.

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