A method for synthesizing an aromatic primary amine compound
By directly constructing C(sp2)-N bonds under visible light using acrid salt and cobalt oxime complex catalysts, the problems of noble metal catalysis and the introduction of directing groups in existing technologies are solved, and a mild, safe and efficient synthesis of primary amination reactions of aromatic hydrocarbons is achieved.
Patent Information
- Application Number
- CN202410963005.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-18
- Publication Date
- 2026-03-20
- Estimated Expiration
- 2044-07-18
AI Technical Summary
Existing techniques for the direct functionalization of aromatic primary amine compounds via CH bonds require the use of noble metal catalysts and directing groups, which increases the number of reaction steps, reduces atom economy and step economy, and the reaction conditions are not mild enough, resulting in environmental problems.
Using acridine salt and cobalt oxime complex as catalysts, aromatic hydrocarbon compounds react with ammonium salts under visible light to construct C(sp2)-N bonds and generate aromatic primary amine compounds. This avoids the use of precious metals and the introduction of directing groups, and the reaction conditions are mild, safe and green.
The primary amination reaction of aromatic hydrocarbons was achieved under mild conditions, exhibiting atom economy and step economy, reducing costs and improving the safety and environmental friendliness of the reaction.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of organic synthesis technology, and in particular to a method for synthesizing aromatic primary amine compounds. Background Technology
[0002] Aromatic primary amines are important intermediates in the synthesis of pharmaceuticals, materials, and fine chemicals, and have significant applications in organic synthesis fields such as medicine and pesticides. Traditional techniques for preparing aromatic primary amines require multiple steps, including nitration of aromatic hydrocarbons and reduction of nitro groups. These techniques suffer from problems such as the use of corrosive raw materials, complex production equipment, numerous byproducts, and environmental unfriendliness. Transition metal-catalyzed coupling reactions of aryl halides with amination reagents, such as the Buchwald-Hartwig, Ullmann, and Chan-Lam coupling reactions, are another effective method for preparing aromatic primary amines. However, these reactions require prefunctionalization of the substrate and inevitably produce a certain amount of halogenated byproducts.
[0003] The synthesis of aromatic primary amines via CH bond functionalization is a highly attractive synthetic method. This method reduces the pre-functionalization of various reagents and starting materials, offering advantages such as fewer steps, high atom economy, and simple operation. However, existing techniques for the direct functionalization of aromatic primary amines via CH bonds require the use of noble metal catalysts and directing groups. The introduction and removal of these directing groups increase the number of reaction steps, reducing atom economy and step economy. Therefore, there is an urgent need to provide a method to improve upon these problems. Summary of the Invention
[0004] The purpose of this invention is to provide a method for synthesizing aromatic primary amine compounds, which constructs C(sp) compounds by functionalizing the CH bond. 2 The reaction utilizes the -N bond to achieve primary amination of aromatic hydrocarbons. The reaction conditions are mild, the operation is simple, safe and green, and no oxidant is required. It has atom economy and step economy, which is in line with the concept of green development.
[0005] The present invention provides a method for synthesizing aromatic primary amine compounds, wherein aromatic hydrocarbon compounds react with ammonium salts under visible light in a solvent system and a non-oxidizing atmosphere, under the action of a catalyst, to generate aromatic primary amine compounds; the catalyst includes acridine salts and cobalt oxime complexes.
[0006] The synthetic method provided by this invention uses an organic dye acridine salt and a cobalt oxime complex as a catalyst. The reaction substrate does not require activation. A safe, stable, inexpensive, and readily available ammonium salt is used as the amine source. Under a non-oxidizing atmosphere and visible light irradiation, the CH bond is functionalized to construct C(sp...)... 2The method utilizes the -N bond to achieve primary amination of aromatic hydrocarbons. This method features mild reaction conditions, simple operation, safety, and environmental friendliness, requires no oxidant, and exhibits atom and step economy, aligning with the principles of green development.
[0007] Optionally, the catalyst comprises an acridine salt and a cobalt oxime complex in a mass ratio of 1:(1-2).
[0008] Optionally, the acridine salt includes at least one of 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onium tetrafluoroborate and 3,6-di-tert-butyl-9-trimethyl-10-methylacridin-10-onium tetrafluoroborate.
[0009] Optionally, the cobalt oxime complex includes at least one of Co(dmgH)(dmgH2)Cl2 and Co(dmgH)2PyCl.
[0010] Optionally, the aromatic hydrocarbon compound includes at least one of naphthalene compounds, benzene compounds, quinoline compounds, isoquinoline compounds, fluorene compounds, and phenanthrene compounds.
[0011] Optionally, the ammonium salt includes at least one of ammonium carbonate, ammonium bicarbonate, ammonium chloride, urea, and ammonium sulfate.
[0012] Optionally, the concentration of the ammonium salt in the solvent system is 0.0002 mol / L to 1 mol / L.
[0013] Optionally, the concentration of the aromatic hydrocarbon compound in the solvent system is greater than or equal to 1 × 10⁻⁶. -5 mol / L.
[0014] Optionally, the ammonium salt is provided in excess of the aromatic hydrocarbon compound in the solvent system.
[0015] Optionally, the concentration of the catalyst in the solvent system is 0.001 mol / L to 1 mol / L.
[0016] Optionally, the molar ratio of the aromatic hydrocarbon compound to the catalyst in the solvent system is (1-100):1.
[0017] Optionally, the non-oxidizing atmosphere includes at least one of a nitrogen atmosphere and an inert atmosphere.
[0018] Optionally, the solvent system includes an organic solvent, and the organic solvent includes at least one of acetonitrile, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, dichloromethane, 1,2-dichloroethane, methanol, ethanol, and isopropanol.
[0019] Optionally, the wavelength of the visible light is 300nm-800nm.
[0020] Optionally, the visible light source includes one of LED, xenon lamp, mercury lamp, or the sun.
[0021] Optionally, the aromatic hydrocarbon compound reacts with an ammonium salt at 20-30°C under visible light to generate an aromatic primary amine compound.
[0022] Optionally, the process includes the following steps: dissolving the catalyst in a solvent system to obtain a mixed solution; dissolving the aromatic hydrocarbon compound and the ammonium salt in the mixed solution, and reacting them under a non-oxidizing atmosphere and visible light to generate an aromatic primary amine compound. Attached Figure Description
[0023] Figure 1 The above is the 1H NMR spectrum of 1-naphthylamine synthesized in Example 1 of this invention;
[0024] Figure 2 This is the carbon NMR spectrum of 1-naphthylamine synthesized in Example 1 of this invention. Detailed Implementation
[0025] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise defined, the technical or scientific terms used herein should have the ordinary meaning understood by those skilled in the art to which this invention pertains.
[0026] This invention provides a method for synthesizing aromatic primary amine compounds, comprising reacting an aromatic hydrocarbon compound with an ammonium salt under visible light in a solvent system and a non-oxidizing atmosphere, under the action of a catalyst, to generate an aromatic primary amine compound. With the ammonium salt as the amine source, visible light irradiation, and the action of a catalyst, the CH bonds on the aromatic hydrocarbon compound are functionalized to construct C(sp...)... 2 The -N bond is broken, thereby generating aromatic primary amine compounds.
[0027] In fact, the catalyst includes acridine salts and cobalt oxime complexes. Acridine salts are organic dyes. Acridine salts are used as photocatalysts, and cobalt oxime complexes are used to interact with acridine salts, thereby functionalizing the CH bonds on aromatic hydrocarbon compounds under light irradiation.
[0028] In fact, under the action of acridine salt and cobalt oxime complex, the photo-excited acridine salt oxidizes aromatic hydrocarbon compounds into aryl radical cations, while amine compounds undergo nucleophilic substitution reactions with aryl radical cations to obtain nitrogen-bonded aryl radical active substances. These substances can be dehydrogenated under the action of cobalt to finally obtain aromatic amine compounds.
[0029] In some embodiments, the catalyst comprises an acridine salt and a cobalt oxime complex in a mass ratio of 1:(1-2).
[0030] In fact, acridine salts include at least one of 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onium tetrafluoroborate and 3,6-di-tert-butyl-9-trimethyl-10-methylacridin-10-onium tetrafluoroborate.
[0031] Specifically, the structure of 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onium tetrafluoroborate is shown in the following formula:
[0032]
[0033] Specifically, the structure of 3,6-di-tert-butyl-9-trimethyl-10-methylacridin-10-onium tetrafluoroborate is shown in the following formula:
[0034]
[0035] In fact, both 3,6-di-tert-butyl-9-trimethylmethyl-10-phenylacridin-10-onium tetrafluoroborate and 3,6-di-tert-butyl-9-trimethylmethyl-10-methylacridin-10-onium tetrafluoroborate can be synthesized in pure form using commercially available conventional products or in the laboratory using conventional synthetic methods.
[0036] In fact, cobalt oxime complexes include one of Co(dmgH)(dmgH2)Cl2 and Co(dmgH)2PyCl.
[0037] Specifically, the structure of Co(dmgH)(dmgH2)Cl2 is shown in the following formula:
[0038]
[0039] Specifically, the structure of Co(dmgH)₂PyCl is shown in the following formula:
[0040]
[0041] Similarly, both Co(dmgH)(dmgH2)Cl2 and Co(dmgH)2PyCl can be synthesized using commercially available conventional products, or they can be synthesized in pure form in the laboratory using conventional synthetic methods.
[0042] In some embodiments, the aromatic hydrocarbon compound includes at least one of naphthalene compounds, benzene compounds, quinoline compounds, isoquinoline compounds, fluorene compounds, and phenanthrene compounds.
[0043] Specifically, the structure of naphthalene compounds is shown in the following formula:
[0044]
[0045] R1 and R2 are independently hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, ester, carbonyl, aldehyde, carboxyl, hydroxyl, amide, phenyl, cyano, or nitro.
[0046] Specifically, when naphthalene compounds react with ammonium salts under visible light and a catalyst to form naphthylamine compounds, the reaction equation is as follows:
[0047]
[0048] Specifically, the structures of benzene compounds are shown in the following formula:
[0049]
[0050] Among them, R3, R4, R5 and R6 are independently hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, ester, carbonyl, aldehyde, carboxyl, hydroxyl, amide, phenyl, cyano or nitro.
[0051] Specifically, when benzene compounds react with ammonium salts under visible light and a catalyst to form aniline compounds, the reaction equation is as follows:
[0052]
[0053] Specifically, the structure of quinoline compounds is shown in the following formula:
[0054]
[0055] Among them, R7, R8, R9, R 10 and R 11 They are independently hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, ester, carbonyl, aldehyde, carboxyl, hydroxyl, amide, phenyl, cyano, or nitro.
[0056] Specifically, when quinoline compounds react with ammonium salts under visible light and a catalyst to form quinolineamine compounds, the reaction equation is as follows:
[0057]
[0058] Specifically, the structures of isoquinoline compounds are shown in the following formula:
[0059]
[0060] Among them, R 12 It can be hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, ester, carbonyl, aldehyde, carboxyl, hydroxyl, amide, phenyl, cyano, or nitro.
[0061] Specifically, when isoquinoline compounds react with ammonium salts under visible light and a catalyst to form isoquinoline amine compounds, the reaction equation is as follows:
[0062]
[0063] Specifically, the structures of fluorene compounds are shown in the following formula:
[0064]
[0065] Among them, R 13 It can be hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, ester, carbonyl, aldehyde, carboxyl, hydroxyl, amide, phenyl, cyano, or nitro.
[0066] Specifically, when fluorene compounds react with ammonium salts under visible light and a catalyst to form fluoreneamine compounds, the reaction equation is as follows:
[0067]
[0068] Specifically, the structures of phenanthrene compounds are shown in the following formula:
[0069]
[0070] Among them, R 14 It can be hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, ester, carbonyl, aldehyde, carboxyl, hydroxyl, amide, phenyl, cyano, or nitro.
[0071] Specifically, when phenanthrene compounds react with ammonium salts under visible light and a catalyst to form phenanthrene amine compounds, the reaction equation is as follows:
[0072]
[0073] In some embodiments, the ammonium salt includes at least one of ammonium carbonate, ammonium bicarbonate, ammonium chloride, urea, and ammonium sulfate. In fact, by using inexpensive and readily available ammonium salts as amine sources in the reaction, the reaction cost and reaction safety can be effectively reduced.
[0074] In some embodiments, the concentration of ammonium salt in the solvent system is 0.0002 mol / L to 1 mol / L.
[0075] In some embodiments, the concentration of aromatic hydrocarbon compounds in the solvent system is greater than or equal to 1 × 10⁻⁶. -5 mol / L, in reality, the concentration of aromatic hydrocarbons in the solvent system can be 1×10⁻⁶. -5 mol / L - any concentration value within the saturation concentration range. In reality, even after the aromatic hydrocarbon concentration in the solvent system has reached saturation, aromatic hydrocarbons can still be added to the solvent system, but this method has low theoretical economic value.
[0076] In some embodiments, an excess of ammonium salt relative to aromatic hydrocarbons is provided in the solvent system, which is beneficial for the forward reaction of the formation of aromatic primary amines, thereby increasing the yield of aromatic primary amines. In addition, using inexpensive and readily available ammonium salts to increase the conversion rate of aromatic hydrocarbons is beneficial for improving atom economy and reducing reaction costs.
[0077] In some embodiments, the concentration of the catalyst in the solvent system is 0.001 mol / L to 1 mol / L.
[0078] In some embodiments, the molar ratio of aromatic hydrocarbon compound to catalyst in the solvent system is (1-100):1.
[0079] In some embodiments, the non-oxidizing atmosphere includes a nitrogen atmosphere and an inert atmosphere, wherein the inert atmosphere includes at least one of a helium atmosphere, a neon atmosphere, and an argon atmosphere. In practice, the non-oxidizing atmosphere for the formation of aromatic primary amine compounds is an atmospheric pressure atmosphere.
[0080] In some embodiments, the solvent system includes an organic solvent, or a mixture of an organic solvent and water in any proportion, wherein the organic solvent includes at least one selected from acetonitrile, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, dichloromethane, 1,2-dichloroethane, methanol, ethanol, and isopropanol. In practice, the organic solvent can be selected from those commonly used in the art for carrying out the relevant reactions, provided that it can dissolve the reactants, catalyst, and products without reacting with them.
[0081] In some embodiments, the wavelength of visible light is 300nm-800nm.
[0082] In some embodiments, the visible light source includes one of LED, xenon lamp, mercury lamp, or the sun.
[0083] In some embodiments, the aromatic hydrocarbon compound reacts with an ammonium salt at 20-30°C under visible light to generate an aromatic primary amine compound.
[0084] In fact, the method for synthesizing aromatic primary amines provided by this invention includes the following steps:
[0085] S1. Dissolve the catalyst in a solvent system to prepare a mixed solution;
[0086] S2. Aromatic hydrocarbon compounds and ammonium salts are dissolved in a mixed solution and reacted under a non-oxidizing atmosphere and visible light to generate aromatic primary amine compounds.
[0087] Specifically, after the aromatic primary amine compound is generated in step S2, the aromatic primary amine compound can be separated using purification and separation methods commonly used in the art, including but not limited to vacuum concentration and column chromatography.
[0088] Example 1
[0089] Example 1 provides a method for synthesizing an aromatic primary amine compound, comprising the following steps:
[0090] S1. 0.005 mmol 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onium tetrafluoroborate (CAS: 1810004-87-5), 0.005 mmol Co(dmgH)(dmgH2)Cl2 (CAS: 23638-66-6) and 3 mL 1,2-dichloroethane were added to a 10 mL test tube and stirred to prepare a mixed solution.
[0091] S2. 0.1 mmol naphthalene and 0.4 mmol ammonium carbonate were added to the mixed solution and mixed. The mixture was stirred and reacted for 20 h under nitrogen atmosphere and LED blue light (λ = 440 nm). The solvent was evaporated and the product 1-naphthylamine was separated by silica gel column chromatography. The yield was calculated to be 96%.
[0092] The 1-naphthylamine prepared in Example 1 was characterized by 1H NMR and 1C NMR spectra as follows: Figure 1 , Figure 2 As shown.
[0093] Example 2
[0094] Example 2 provides a method for synthesizing an aromatic primary amine compound. The difference from Example 1 is that the amount of Co(dmgH)(dmgH2)Cl2 added in step S1 is 0.01 mmol, and the yield is calculated to be 95% in step S2.
[0095] Example 3
[0096] Example 3 provides a method for synthesizing an aromatic primary amine compound. The difference from Example 1 is that 3 mL of acetonitrile is used instead of 3 mL of 1,2-dichloroethane in step S1, and the yield is calculated to be 31% in step S2.
[0097] Example 4
[0098] Example 4 provides a method for synthesizing an aromatic primary amine compound. The difference from Example 1 is that 3 mL of dichloromethane is used instead of 3 mL of 1,2-dichloroethane in step S1, and the yield is calculated to be 42% in step S2.
[0099] Example 5
[0100] Example 5 provides a method for synthesizing an aromatic primary amine compound. The difference from Example 1 is that 0.005 mmol Co(dmgH)2PyCl (CAS: 23295-32-1) is used instead of Co(dmgH)(dmgH2)Cl2 in step S1, and the yield is calculated to be 55% in step S2.
[0101] Example 6
[0102] Example 6 provides a method for synthesizing an aromatic primary amine compound. The difference from Example 1 is that 0.4 mmol ammonium bicarbonate is used instead of 0.4 mmol ammonium carbonate in step S2, and the yield is calculated to be 70% in step S2.
[0103] Examples 7 to 36
[0104] Examples 7 to 36 provide a method for synthesizing aromatic primary amine compounds, which differ from Example 1 in that the aromatic hydrocarbon compounds are different, as shown in Table 1 below.
[0105] Table 1. Structural formulas and product yields of aromatic hydrocarbon compounds in Examples 7 to 36
[0106]
[0107]
[0108]
[0109]
[0110]
[0111]
[0112]
[0113] Comparative Example 1
[0114] Comparative Example 1 provides a method for synthesizing an aromatic primary amine compound, which differs from Example 1 in that 0.005 mmol Co(dmgH)(dmgH2)Cl2 was not added in step S1, and the yield was calculated to be 0% in step S2.
[0115] Comparative Example 2
[0116] Comparative Example 2 provides a method for synthesizing an aromatic primary amine compound, which differs from Example 1 in that 0.005 mmol of 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onthium tetrafluoroborate was not added in step S1, and the yield was calculated to be 0% in step S2.
[0117] While embodiments of the present invention have been described in detail above, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. However, it should be understood that such modifications and variations fall within the scope and spirit of the invention as set forth in the claims. Furthermore, the invention described herein may have other embodiments and can be implemented or carried out in various ways.
Claims
1. A method for synthesizing an aromatic primary amine compound, characterized in that, In an organic solvent system and a non-oxidizing atmosphere, under the action of a catalyst, aromatic hydrocarbons react with ammonium salts under visible light to generate aromatic primary amine compounds. The catalyst comprises an acridine salt and a cobalt oxime complex in a mass ratio of 1:(1-2). The acridine salt is 3,6-di-tert-butyl-9-trimethyl-10-phenylacridin-10-onium tetrafluoroborate, and the cobalt oxime complex is selected from at least one of Co(dmgH)(dmgH2)Cl2 and Co(dmgH)2PyCl. The organic solvent is selected from one of 1,2-dichloroethane, acetonitrile, and dichloromethane. The non-oxidizing atmosphere is an inert atmosphere. The ammonium salt is selected from one of ammonium carbonate and ammonium bicarbonate. The aromatic hydrocarbon is selected from at least one of naphthalene compounds, benzene compounds, quinoline compounds, isoquinoline compounds, fluorene compounds, and phenanthrene compounds. Among them, the reaction equation for the formation of naphthylamine compounds from naphthalene compounds by reacting with ammonium salts under visible light and a catalyst is as follows: ； R1 and R2 are independently hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, aldehyde, carboxyl, hydroxyl, phenyl, cyano, or nitro. Alternatively, when benzene compounds react with ammonium salts under visible light and a catalyst to form aniline compounds, the reaction equation is: ； R3, R4, R5 and R6 are independently hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, aldehyde, carboxyl, hydroxyl, phenyl, cyano or nitro. Alternatively, when quinoline compounds react with ammonium salts under visible light and a catalyst to form quinolineamine compounds, the reaction equation is as follows: ； R7, R8, R9, R 10 and R 11 They are independently hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, aldehyde, carboxyl, hydroxyl, phenyl, cyano, or nitro. Alternatively, when isoquinoline compounds react with ammonium salts under visible light and a catalyst to form isoquinoline amine compounds, the reaction equation is: ； R 12 It can be hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, aldehyde, carboxyl, hydroxyl, phenyl, cyano, or nitro; Alternatively, when fluorene compounds react with ammonium salts under visible light and a catalyst to form fluoreneamine compounds, the reaction equation is as follows: ； R 13 It can be hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, aldehyde, carboxyl, hydroxyl, phenyl, cyano, or nitro; Alternatively, when phenanthrene compounds react with ammonium salts under visible light and a catalyst to form phenanthrene amine compounds, the reaction equation is: ； R 14 It can be hydrogen, alkyl, alkoxy, fluorine, chlorine, bromine, trifluoromethyl, aldehyde, carboxyl, hydroxyl, phenyl, cyano, or nitro.
2. The synthesis method according to claim 1, characterized in that, The concentration of the ammonium salt in the solvent system is 0.0002 mol / L to 1 mol / L; and / or, the concentration of the aromatic hydrocarbon compound in the solvent system is greater than or equal to 1 × 10⁻⁶. - 5 mol / L; and / or, in the solvent system, the ammonium salt is provided in excess relative to the aromatic hydrocarbon compound.
3. The synthesis method according to claim 1, characterized in that, The concentration of the catalyst in the solvent system is 0.001 mol / L to 1 mol / L; and / or, the molar ratio of the aromatic hydrocarbon compound to the catalyst in the solvent system is (1-100):
1.
4. The synthesis method according to claim 1, characterized in that, The inert atmosphere includes a nitrogen atmosphere.
5. The synthesis method according to claim 1, characterized in that, The wavelength of the visible light is 300nm-800nm; and / or the light source of the visible light includes one of LED, xenon lamp, mercury lamp, and the sun.
6. The synthesis method according to claim 1, characterized in that, The aromatic hydrocarbon compound reacts with ammonium salt at 20-30°C under visible light to generate an aromatic primary amine compound.
7. The synthesis method according to any one of claims 1 to 6, characterized in that, Includes the following steps: A mixed solution is prepared by dissolving the catalyst in a solvent system; an aromatic hydrocarbon compound and an ammonium salt are dissolved in the mixed solution, and the mixture is reacted under a non-oxidizing atmosphere and visible light to generate an aromatic primary amine compound.