RU2213727C2 - Method for preparing tertiary adamantane alcohol acrylate and methacrylate - Google Patents

Abstract

FIELD: organic chemistry, chemical technology. SUBSTANCE: invention relates to the improved method for preparing acrylates and methacrylates of tertiary alcohols of adamantine order that are used as parent compounds for polymeric materials for 193 nm laser microlithography in making semiconductive devices. Method involves interaction of adamantanone-2 with alkylmagnesium halide followed by successive addition to reaction mixture of tertiary organic base, derivative if acrylic or methacrylic acid and water and the following filtration of precipitate of formed inorganic salts and isolation of end compounds. Method involves usage of alkylmagnesium halides of the general formula AlkMgHal wherein Hal is J, Br, Cl; Alk is -CH₃,C₂H₅,n-C₃H₇,i-C₃H₇,n-C₄H₉. Bases taken among the group: triethylamine, tributylamine, diethylbenzylamine, pyridine, 5-(N,N-dimethylamino)- pyridine or N, N-dimethylaniline are used tertiary organic base. Reaction is carried out at temperature 0-10 C in the presence of anhydrous metal halide taken among the group: TiCl₄,AlHal₃,MgHal₂,FeHal₃,SnCl₄ and the following interaction with anhydride or halogen-anhydride as derivative of acrylic or methacrylic acid at 0-80 C in the weight ratio adamanatanone-2 : alkylmagnesium halide : metal halide : organic base : derivative of acrylic or methacrylic acid = 1 : (0.7-2.4) : (0-1.0) : (0.06-2.0) : (0.7-3.0), respectively. Amount of added water is 0.17-0.74 weight part per the parent adamantanone-2. Invention provides to elevate selectivity, to simplify technological process and to reduce amount of flows. EFFECT: improved preparing method. 10 ex

Description

 The invention relates to a method for producing acrylic and methacrylic esters of sterically hindered alcohols of the adamantane series used as starting compounds for polymeric materials for 193 nm laser microlithography in the manufacture of semiconductor devices.

A number of methods for the synthesis of such compounds are known:
1) by the reaction of tertiary adamantane alcohols with methacryloyl chloride in tetrahydrofuran in the presence of triethylamine (EP 0999474 from 05.10.2000),
2) the interaction of 2-methyl-2-adamantanol with methacrylic acid chloride in the presence of methyl isobutyl ketone and triethylamine (EP 1020767 from 07.19.2000, EP 0982628 A2 from 01.03.2000),
3) by reaction of 2-adamantanone with an ethereal solution of ethyl lithium, followed by the addition of methacryloyl chloride to the reaction mixture (EP 1020767 from 07/19/2000, EP 0982628 A2 from 03/01/2000).

 However, the above methods require the use of hard-to-reach tertiary alcohols as starting compounds, highly toxic and expensive unsaturated acid halides, solvents and catalysts, which limits the scope and reduces the economic efficiency of these methods.

 The closest in technical essence to the claimed method is a method for producing tertiary alcohol esters by esterification of ketones with unsaturated acid halides in the presence of Grignard reagents in an environment of organic solvents, followed by decomposition of the reaction mixture with water and isolation of the target products by silica gel column chromatography (JP 2000229911 from 08.22.2000) .

The specified method has a number of significant disadvantages:
1) the preparation of methacrylates with larger than methyl alkyl substituents at the carbon atom of the ester bond is not possible according to the specified method. This is due to the noticeable predominance of the side reaction of the reduction of the carbonyl group of ketones when interacting with higher alkyl magnesium halides (in the case when the organomagnesium compound has a beta-hydrogen atom capable of moving to carbonyl carbon through a six-membered transition state (General Organic Chemistry, edited by D. Burton and D. Ollis, v. 7, p. 52, M., "Chemistry", 1984)). For example, in the reaction of adamantanone with n-butylmagnesium bromide, the formation of 2-adamantanone with a yield of up to 90% is observed (S. Landa et al., Coll. Czech. Chem. Commun., 1967, 32, p. 570) (see comparative example 1);
2) the formation of significant quantities of undesirable impurities in the raw product, which requires the use of purification of the target methacrylate to the required quality parameters by preparative liquid chromatography on silica gel, which significantly reduces the possibility of industrial application of the method due to the significant complexity and cost of the process;
3) a significant amount of effluents containing tetrahydrofuran and methacrylic acid, as well as the use of an inert atmosphere in the synthesis process, which requires additional investments in the production infrastructure;
4) the exclusive use of an expensive and extremely toxic methacrylic acid chloride as an acylating agent.

 The technical result of the invention is to simplify the process and reduce the amount of effluent.

The technical result is achieved by the fact that the method of producing acrylates and methacrylates of tertiary alcohols of the adamantane series by the reaction of adamantanone-2 with an alkyl magnesium halide followed by sequential addition of a tertiary organic base and an acrylic or methacrylic acid derivative to the reaction mixture. The reaction of adamantanone-2 includes alkyl magnesium halides of the general formula AlkMgHal (where Hal = J, Br, Cl; Alk = CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , iC ₃ H ₇ , n-C ₄ H ₉ ), as a tertiary organic base, bases selected from the group are used: triethylamine, tributylamine, diethylbenzylamine, pyridine, 4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline, at a temperature of 0-10 ^o C, and the reaction is carried out in the presence of anhydrous metal halide selected from the group: TiCl ₄ , AlHal ₃ , MgHal ₂ , FeHal ₃ , SnCl ₄ , followed by reaction with a derivative (anhydride or halide) of acrylic or meta krillic acid at 0-80 ^o With a weight ratio of adamantanone-2: alkylmagnesium halide: metal halide: organic base: derivative of acrylic or methacrylic acid, equal to 1: 0.7-2.4: 0-1.0: 0.06- 2.0: 0.7-3.0, and the amount of added water is 0.17-0.74 parts by weight. to the original adamantanon-2.

Features:
- the use of metal salts,
- the use of organic bases,
- adding a small amount of water and removing a precipitate of metal salts from the reaction mass.

The claimed invention has the following advantages:
1) the possibility of obtaining methacrylates with higher alkyl substituents through the use of additives of anhydrous metal halides (Lewis acids). In this case, another organometallic compound is formed directly in the reactor, which changes the geometric parameters of the transition state of the process, due to which the side reduction reaction is suppressed. There is no need to use an inert atmosphere, which simplifies the process;
2) the high quality of the raw material and the possibility of using cheaper and significantly less toxic methacrylic acid anhydride, and not acid chloride. These advantages are provided through the use of an organic base that effectively catalyzes the acylation reaction and increases the selectivity of the process;
3) sufficient quality indicators of the raw product make it possible to avoid purification by such an expensive method as column chromatography;
4) adding water to the reaction mixture at the end of the reaction leads to the formation of a precipitate containing inorganic components of the reaction mass along with the salts of the used organic base and acrylic or methacrylic acid. The separation of solid sediment allows to solve the problems:
- disposal of organic solvent;
- sewage treatment;
- the presence of not containing adamantane fragment of organic impurities in the raw product.

Examples of the method
I. Synthesis of 2-methyl-2-adamantyl methacrylate
12 g of magnesium, 50 ml of THF (abs.) And a crystal of iodine are loaded into a 1 L flask. Then 160 ml of a 38% solution of methyl bromide are added dropwise at a temperature of 25-35 ^° C. The reaction mixture is stirred at 25 ^{° C.} until the magnesium is completely dissolved. A solution of 50 g of 2-adamantanone in 200 ml of THF at 25 ^{° C. is} added dropwise to the resulting solution of methylmagnesium bromide for 45 minutes, then the reaction mixture is stirred at the same temperature for 1 hour. After this, 24 ml of triethylamine are added to the flask and 42 ml of methacryloyl chloride are added dropwise. , stirred at 20 ^o C for 5 hours, add 9 ml of water, the precipitate is filtered off and THF is distilled off. After this, 400 ml of water and 200 ml of toluene are added, after stirring, the toluene layer is separated, washed with water and the toluene is distilled off in vacuo. The crude is distilled in vacuum, collecting the fraction with T. boil. 150-151 ^o C / 9 mm RT. Art. 53 g (68%) of 2-methyl-2-adamantylmethacrylate are obtained, n _D ²⁰ = 1.4980.

IR spectrum, cm ^-1 : 2890, 1725, 1635, 1450, 1310, 1160, 945.

 Found,%: C 76.61%, H 9.52.

C ₁₅ H ₂₂ O ₂ .

 Calculated,%: C 76.88%, H 9.46.

II. Synthesis of 2-ethyl-2-adamantyl acrylate
Into a 1 L flask was charged 9.6 g of magnesium, 50 ml of ether (abs.) And a crystal of iodine. Then, 150 ml of a 20% solution of ethyl chloride are added dropwise at a temperature of 5-10 ^° C. The reaction mixture is stirred at 10 ^{° C.} until the magnesium is completely dissolved. To the resulting solution of ethyl magnesium chloride add 5.5 g of magnesium chloride (or 10.6 g of MgBr ₂ ) and a solution of 50 g of 2-adamantanone in 150 ml of methylene chloride is added dropwise at 10-20 ^° C for 30 minutes, then the reaction mass is stirred at that at the same temperature for 2 hours. After this, 9 g of N, N-dimethylaniline was added to the flask, and 60 ml of acrylic acid anhydride were added dropwise, stirred at 0 ^° C for 2 hours, 9 ml of water was added, the precipitate was filtered off and the solvent was distilled off. After this, 450 ml of water and 180 ml of benzene are added, after stirring, the benzene layer is separated, washed with water and the benzene is distilled off in vacuo. The crude is distilled in vacuo, collecting the fraction with T. bales. 154-155 ^o C / 9 mm RT. Art. 60 g (77%) of 2-ethyl-2-adamantyl acrylate are obtained, n _D ²⁰ 1.5071.

IR spectrum, cm ^-1 : 2890, 1725, 1635, 1450, 1310, 1160, 945.

 Found,%: C 76.98, H 9.58.

C ₁₅ H ₂₂ O ₂ .

 Calculated,%: C 76.88, H 9.46.

III. Synthesis of 2-ethyl-2-adamantyl methacrylate
Into a 1 L flask was charged 9.6 g of magnesium, 50 ml of ether (abs.) And a crystal of iodine. Then, 150 ml of a 20% solution of ethyl bromide are added dropwise at a temperature of 5-10 ^° C. The reaction mixture is stirred at 10-15 ^{° C.} until the magnesium is completely dissolved. 10 g of AlCl ₃ (or 20 g of AlBr ₃ ) are added to the resulting solution of ethyl magnesium bromide, a solution of 50 g of 2-adamantanone in 150 ml of methylene chloride is added dropwise at 10-20 ^° C for 30 minutes, then the reaction mass is stirred at the same temperature for 2 hours. After that, 9 g of N, N-dimethylaniline was added to the flask, and 60 ml of methacryloyl chloride were added dropwise, stirred at 0 ^{° C.} for 2 hours, 22 ml of water was added, the precipitate was filtered off and the solvent was distilled off. After this, 420 ml of water and 250 ml of cyclohexane are added, after stirring, the organic layer is separated, washed with water and the cyclohexane is distilled off in vacuo. The crude is distilled in vacuo, collecting the fraction with T. bales. 167 ^o C / 8 mm RT. Art. Obtain 61 g (74%) of 2-ethyl-2-adamantylmethacrylate, n _D ²⁰ = 1.4976.

IR spectrum, cm ^-1 : 2890, 1725, 1635, 1450, 1310, 1160, 945.

 Found,%: C 77.61, H 9.86.

C ₁₆ H ₂₄ O ₂ .

 Calculated,%: C 77.38, H 9.74.

IV. Synthesis of 2-propyl-2-adamantyl methacrylate
In a 1 L flask, 17 g of magnesium, 150 ml of ether (abs.) And a crystal of iodine are charged. Then, 122 g of propyl iodide are added dropwise at a temperature of 25-30 ^° C. The reaction mixture is stirred at 30 ^{° C.} until the magnesium is completely dissolved. To the resulting solution of propyl magnesium iodide, 38 g of TiCl ₄ are added and a solution of 50 g of 2-adamantanone in 150 ml of methylene chloride is added dropwise at 10-20 ^{° C.} for 2 hours, then the reaction mass is stirred at the same temperature for 3 hours. After that, the flask is 100 ml of pyridine are added, and 200 ml of methacryloyl bromide are added dropwise, stirred at 30 ^{° C.} for 10 hours, 30 ml of water are added, the precipitate is filtered off and the solvent is distilled off. After this, 450 ml of water and 250 ml of benzene are added, after stirring, the organic layer is separated, washed with water and the benzene is distilled off in vacuo. The crude is distilled in vacuum, collecting the fraction with T. boil. 180-181 ^o C / 8 mm RT. Art. Obtain 70 g (80%) of 2-propyl-2-adamantylmethacrylate, n _D ²⁰ = 1.4974.

IR spectrum, cm ^-1 : 2890, 1725, 1635, 1450, 1310, 1160, 945.

 Found,%: C 77.51, H 9.88.

C ₁₇ H ₂₆ O ₂ .

 Calculated,%: C 77.82, H 9.99.

V. Synthesis of 2-propyl-2-adamantyl acrylate
In a 1 L flask, 17 g of magnesium, 150 ml of ether (abs.) And a crystal of iodine are charged. Then, 122 g of propyl iodide are added dropwise at a temperature of 25-30 ^° C. The reaction mixture is stirred at 30 ^{° C.} until the magnesium is completely dissolved. To the resulting solution of propyl magnesium iodide, 38 g of TiCl ₄ are added and a solution of 50 g of 2-adamantanone in 150 ml of methylene chloride is added dropwise at 10-20 ^{° C.} for 2 hours, then the reaction mass is stirred at the same temperature for 3 hours. After that, the flask is 100 ml of pyridine are added, and 180 ml of acryloyl bromide are added dropwise, stirred at 30 ^{° C.} for 10 hours, 30 ml of water are added, the precipitate is filtered off and the solvent is distilled off. After this, 500 ml of water and 300 ml of cyclohexane are added, after stirring, the organic layer is separated, washed with water and the cyclohexane is distilled off in vacuo. The crude is distilled in vacuo, collecting the fraction with T. bales. 168-170 ^o C / 8 mm RT. Art. 65 g (79%) of 2-propyl-2-adamantyl acrylate are obtained, n _D ²⁰ = 1.4977.

IR spectrum, cm ^-1 : 2890, 1725, 1635, 1450, 1310, 1160, 945.

 Found,%: C 77.56, H 9.91.

C ₁₆ H ₂₄ O ₂ .

 Calculated,%: C 77.38, H 9.74.

VI. Synthesis of 2-i-propyl-2-adamantyl methacrylate
17 g of magnesium, 150 ml of anisole (abs.) And a crystal of iodine are loaded into a 1 L flask. Then, 122 g of i-propyl iodide are added dropwise at a temperature of 50 ^° C. The reaction mixture is stirred at 50 ^{° C.} until the magnesium is completely dissolved. To the resulting solution of i-propylmagnesium iodide was added 5 g of SnCl ₄ and a solution of 50 g of 2-adamantanone in 200 ml of anisole was added dropwise at 60 ^{° C.} for 2 hours, then the reaction mixture was stirred at the same temperature for 3 hours. After that, add to the flask 18 g of 4- (N, N-dimethylamino) pyridine and 45 ml of methacryloyl chloride are added dropwise, stirred at 80 ^{° C.} for 15 hours, another 15 ml of methacrylchloride are added and stirred at the same temperature for another 10 hours, 18 ml of water is added, and the precipitate is filtered off. and the solvent is distilled off. After this, 450 ml of water and 230 ml of toluene are added, after stirring, the toluene layer is separated, washed with water and the toluene is distilled off in vacuo. The crude is distilled in vacuum, collecting the fraction with T. boil. 176-177 ^o C / 8 mm RT. Art. 65 g (74%) of 2-isopropyl-2-adamantylmethacrylate are obtained, n _D ²⁰ = 1.4973.

IR spectrum, cm ^-1 : 2890, 1725, 1635, 1450, 1310, 1160, 945.

 Found,%: C 77.98, H 9.91.

C ₁₇ H ₂₆ O ₂ .

 Calculated,%: C 77.82, H 9.99.

VII. Synthesis of 2-butyl-2-adamantyl methacrylate
17 g of magnesium, 150 ml of anisole (abs.) And a crystal of iodine are loaded into a 1 L flask. Then, 100 g of n-butyl bromide are added dropwise at a temperature of 50 ^° C. The reaction mixture is stirred at 50 ^{° C.} until the magnesium is completely dissolved. To the resulting solution of n-butylmagnesium bromide was added 3 g of MgJ ₂ (anhydrous) and a solution of 50 g of 2-adamantanone in 200 ml of anisole was added dropwise at 60 ^{° C.} for 1 h, then the reaction mixture was stirred at the same temperature for 2 h. After 3 g of 4- (N, N-dimethylamino) pyridine is added to the flask, and 80 ml of methacryloyl chloride are added dropwise, stirred at 80 ^{° C.} for 30 hours, 18 ml of water are added, the precipitate is filtered off and the solvent is distilled off. After this, 400 ml of water and 250 ml of benzene are added, after stirring, the organic layer is separated, washed with water and the benzene is distilled off in vacuo. The crude is distilled in vacuum, collecting the fraction with T. boil. 179-181 ^o C / 8 mm RT. Art. 54 g (59%) of 2-butyl-2-adamantylmethacrylate are obtained, n _D ²⁰ = 1.4975.

IR spectrum, cm ^-1 : 2890, 1725, 1635, 1450, 1310, 1160, 945.

 Found,%: C 78.07, H 10.27.

C ₁₈ H ₂₈ O ₂ .

 Calculated,%: C 78.21, H 10.21.

Viii. Synthesis of 2-butyl-2-adamantyl acrylate
17 g of magnesium, 150 ml of anisole (abs.) And a crystal of iodine are loaded into a 1 L flask. Then, 100 g of n-butyl bromide are added dropwise at a temperature of 50 ^° C. The reaction mixture is stirred at 50 ^{° C.} until the magnesium is completely dissolved. To the resulting solution of n-butylmagnesium bromide add 50 g of FeCl ₃ (anhydrous) and a solution of 50 g of 2-adamantanone in 200 ml of anisole is added dropwise at 60 ^{° C.} for 1 hour. The reaction mass is stirred at the same temperature for 2 hours. After that 3 g of 4- (N, N-dimethylamino) pyridine are added to the flask, and 80 ml of acryloyl chloride are added dropwise, stirred at 80 ^{° C.} for 20 hours, 33 ml of water are added, the precipitate of hydrated metal salts is filtered off and the solvent is distilled off. After this, 500 ml of water and 200 ml of cyclohexane are added, after stirring, the organic layer is separated, washed with water and the cyclohexane is distilled off in vacuo. The crude is distilled in vacuum, collecting the fraction with T. boil. 171-172 ^o C / 8 mm RT. Art. 57 g (65%) of 2-butyl-2-adamantyl acrylate are obtained, n _D ²⁰ = 1.4981.

IR spectrum, cm ^-1 : 2890, 1725, 1635, 1450, 1310, 1160, 945.

 Found,%: C 77.97, H 9.92.

C ₁₇ H ₂₆ O ₂ .

 Calculated,%: C 77.82, H 9.99.

IX. Synthesis of 1- (1-adamantyl) -1-methylethyl 2-methacrylate
In a 1 L flask, 11 g of magnesium, 50 ml of THF (abs.) And crystalline iodine are charged. Then 140 ml of a 38% methyl bromide solution are added dropwise at a temperature of 25-35 ^° C. The reaction mixture is stirred at 25 ^{° C.} until the magnesium is completely dissolved. A solution of 59 g of methyladamantyl ketone in 100 ml of THF at 25 ^{° C. is} added dropwise to the resulting solution of methylmagnesium bromide for 40-45 minutes, then the reaction mixture is stirred at the same temperature for 1 hour. After this, 7 ml of triethylamine are added to the flask and 35 ml of methacryloyl chloride are added dropwise. , stirred at 25-35 ^o C for 30 minutes, add 9 ml of water, the precipitate is filtered off and THF is distilled off. After this, 500 ml of water and 250 ml of benzene are added, after stirring, the organic layer is separated, washed with water and benzene is distilled off in vacuo. The crude is distilled in vacuo, collecting the fraction with T. bales. 179-181 ^o C / 8 mm RT. Art. Obtain 60 g (72%) of 1- (1-adamantyl) -1-methylethyl 2-methacrylate, n _D ²⁰ = 1,5006.

IR spectrum, cm ^-1 : 2890, 1725, 1635, 1450, 1310, 1170, 965.

 Found,%: C 77.65, H 10.05.

C ₁₇ H ₂₆ O ₂ .

 Calculated,%: C 77.82, H 9.99.

Comparative example 1:
Synthesis of 2-ethyl-2-adamantyl acrylate
10 g of magnesium, 50 ml of ether (abs.) And a crystal of iodine are loaded into a 1 L flask. Then, 150 ml of a 20% solution of ethyl bromide are added dropwise at a temperature of 5-10 ^° C. The reaction mixture is stirred at 25 ^{° C.} until the magnesium is completely dissolved. To the resulting solution of ethyl magnesium bromide was added a solution of 50 g of 2-adamantanone in 150 ml of methylene chloride at 25 ^° C for 30 minutes, then the reaction mixture was stirred at the same temperature for 1 hour. After that, 7 ml of triethylamine was added to the flask and 40 ml was added dropwise. acryloyl chloride, stirred at 25 ^o C for 10 h, add 17 ml of water, the precipitate is filtered off and the solvent is distilled off. After this, 450 ml of water and 250 ml of toluene are added, after stirring, the toluene layer is separated, washed with water and the toluene is distilled off in vacuo. The GLC residue consists of a mixture of 2-ethyl-2-adamantyl acrylate and 2-adamantyl acrylate in a ratio of 35:65, respectively, yield 63 g.

Claims (1)

The method of producing acrylates and methacrylates of tertiary alcohols of the adamantane series by reacting adamantanone-2 with an alkyl magnesium halide followed by sequential addition of a tertiary organic base derived from acrylic or methacrylic acid and water to the reaction mixture, followed by filtering the precipitate of the obtained inorganic salts and isolating the target products, characterized in that that alkyl magnesium halides of the general formula AlkMgHal are used, where Hal = J, Br, Cl; Alk = CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , i-C ₃ H ₇ , n-C ₄ H ₉ , as the tertiary organic base, bases selected from the group of triethylamine, tributylamine, diethylbenzylamine, pyridine, 4- (N, N-dimethylamino) pyridine or N, N-dimethylaniline, at a temperature of 0-10 ^{° C.} , and the reaction is carried out in the presence of an anhydrous metal halide selected from the group TiCl ₄ , AlHal ₃ , MgHal ₂ , FeHal ₃ , SnCl ₄ , followed by interaction with anhydride or halide, as a derivative of acrylic or methacrylic acid at 0-80 ^o With a weight ratio of adamantanone-2: alkyl agni halide: metal halide: organic base: derivative of acrylic or methacrylic acid, equal to 1: 0.7-2.4: 0-1.0: 0.06-2.0: 0.7-3.0, and the amount added water is 0.17-0.74 parts by weight to the original adamantanon-2.