The method of obtaining functionally substituted methylenecyclobutane

 

(57) Abstract:

Describes how to obtain functionally substituted methylenecyclobutane by interaction Allen derived from ethylene, containing the group-COOH or-COOR, or-CN, at elevated temperature, followed by separation of the reaction products and rectifying the selection of the target product. The difference method is that the source is Allen's use allinaday gas containing Allen 10 to 80%, and as a derivative of ethylene containing a group-COOR, use alkalemia esters with R = C1- C4the process is carried out in the vapor phase at temperatures above 360oC and a pressure of 0.1 - 1.0 MPa to conversion Allen is not above 60%, at the exit of the reactor, the reaction products quenched and separated by distillation, the desired product away as a trademark, unreacted Allen and derived ethylene return in the process. The technical result - improving the performance of the method with its simultaneous simplification. 3 C.p. f-crystals, 1 Il., table 1.

The invention relates to the petrochemical industry and, more specifically, to a method for functionally substituted methylenecyclobutane.

Functionally samisen the rooms in the manufacture of various polymers for special purposes, in the synthesis of biologically active substances and the synthesis of a number of compounds containing cyclobutanone fragments in molecules.

A method of obtaining functionally substituted methylenecyclobutane - anhydride methylenecyclobutane-1,2-dicarboxylic acid (K. Alder and O. Ackermann, Chem.Ber. 90, 1697, 1957) [1]. In accordance with this method, Allen is subjected to interaction with maleic anhydride under pressure ~20 at temperatures of ~250oC, substituted methylenecyclobutane in the calculation loaded Allen is about 20%. This method does not allow to obtain any substituted methylenecyclobutane in addition to the above, i.e., is not universal.

Also known is a method of obtaining methylenecyclobutanecarbonitrile from Allen and Acrylonitrile (F. Caserio, et al, JACS, 80, p.5507-5513, 1958)[2]. The synthesis is carried out in an environment of toluene at 260-270oC yield of the target product ~60%. A process is described for obtaining methylenecyclobutanecarbonitrile, accompanied by a significant resin formation, resulting in unproductive expenditure of reagents and complicates the selection of the target product.

More versatile and the closest to the technical essence of the present invention is a method for online substituted 3-methylenecyclobutane get cyclopentadiene to allenham derivatives of ethylene, the group containing COOH, COOR, CN, CONH2others In the quality of reagents used acrylic and methacrylic acids, NITRILES, amides and lower esters of these acids and other activated olefins. The process is carried out under pressure in a special autoclave, in the liquid phase in the environment of the solvent, in the presence of the polymerization inhibitor is hydroquinone or phenthiazine, or without it. The method is carried out at high conversion of Allen. Used Allen with a purity of ~100%, resulting in fire and explosion. The process is carried out in periodic mode, at a temperature of ~ 150-250oC, depending on the activated ethylene.

Method [3] is characterized by the periodicity of the process, low performance on the target product. The process is quite lengthy and requires special equipment. A significant amount of by-products makes it difficult to select the target methylenecyclobutane. In addition, the implementation of the method cycloaddition of activated olefins to Allen in the liquid phase leads to a gradual decrease in the concentration of reagents in the reaction medium and the falling speed of their transformation.

The present invention, therefore, was with the authorized simplifying the technology of its implementation.

It was found that the objective is formulated, in accordance with the present invention is solved by a method of obtaining functionally substituted methylenecyclobutane by interaction Allen derived from ethylene, containing the group-COOH or-COOR, or-CN, at elevated temperature, followed by separation of the reaction products and the selection of the target product by distillation, characterized in that the source is Allen's use allinaday gas containing Allen 10 to 80%, as derived ethylene, containing the group-COOR, use alkilany ether with R = C1-C4the process is carried out in the vapor phase, at temperatures above 350oC to conversion Allen is not above 60%, at the exit of the reactor, the reaction products quenched and separated by distillation, the desired product away as a trademark, unreacted Allen and derived ethylene return in the process, the process is carried out preferably before the conversion of 20-30% at 400-550oC and a pressure of 1-1,0 MPa, alkilany ether-COOC4- butyl ether radicals of normal, ISO - or tertiary structure.

As raw materials can be used activated ethylene containing the group: -COOH acrylic and methacrylic acids; the process in the vapor phase enables you to ensure a nearly constant ratio of the reacting substances and the homogeneity of the reaction medium, the result is a minimum temperature gradient as the height of the reactor and in the radial direction.

Source Allen can be used methylacetylene fraction with contents Allen 10 - 80% Allen. Other components: methylacetylene, propylene, propane and other phlegmatization. The use of such materials does not affect the quality of target products, you can ensure vzryvopozharobezopasnost process and make it more efficient by reducing the cost of Allen.

The method in accordance with the present invention allows to organize the process in a continuous mode, with almost constant reactant concentrations, and hence a constant speed. The process has a high selectivity and conversion of Allen ~30% of the reactants are consumed mainly to obtain the desired products. The resin formation is minimal. This allows you to retalitate unreacted substances for subsequent use in the process. Quenching of the reaction products at the outlet of the reactor maintains the desired conversion of Allen. Limit conversion of Allen, the top within inost process, and ultimately the yield of the target product. Thus, the set of essential features of the present invention provides for obtaining functionally substituted methylenecyclobutane more productive and profitable than in the prototype, by the way. In the present method of obtaining functionally substituted methylenecyclobutane does not envisage the use of inhibitors, in addition to contained in the sales of raw materials.

Particularly noteworthy is the significant simplification of the hardware design process, control of technological parameters and the selection is received while functionally substituted methylenecyclobutane.

The process is continuous, which creates the undoubted convenience of its industrial development.

For a better understanding of the invention the drawing shows the technological scheme of production of functionally substituted methylenecyclobutane.

Stream derived ethylene I sent to the evaporator 1, the output of which thread I mixed in predetermined proportions with the flow allenstergess II gas and this mixture is introduced into the heater 2. Heated to the required temperature of the raw material mixture is sent forth the Torah 3 is introduced into the quenching apparatus 4, where is the condensation of a part of components of the product mixture. Gas-liquid mixture unit 4 are sent forth into the separator 5, where the share of the gas and liquid phases. The gas phase stream III return in recycling the input stream II, the liquid phase stream IV is directed to the separation in a distillation node 6, where isolated derivative of ethylene V - stream returned in recycling the input stream I, functionally substituted methylenecyclobutane VI, and heavy reaction products VII.

The invention is illustrated with specific examples of performance.

Examples 1, 3. Getting methylenecyclobutane acids.

Stream derived ethylene I - acrylic or methacrylic acid is sent to the heater 1, the output of which thread I mixed in predetermined proportions with the flow allenstergess II gas and this mixture is introduced into the heater 2. Heated to the required temperature of the raw material mixture is sent forth into the reactor 3, which is the cycloaddition of a derivative of ethylene to Allen. Then the reaction mass from the reactor 3 is introduced into the quenching apparatus 4, where the condensation of a part of components of the product mixture. Gas-liquid mixture unit 4 are sent forth in separa the ski operations, return in recycling the input stream II. The liquid phase stream IV is directed to the separation in a distillation node 6. In rectifying the node 6 are: a derivative of ethylene - flow V returned in recycling the input stream I; functionally substituted methylenecyclobutane VI; and the heavy reaction products VII.

The ratio of the products obtained: ~10% 2-methylene - 90% 3-methylenecyclobutane acids. The results are shown in the table.

Example 2*(comparative) Obtaining methylenecyclobutane acids.

Getting methylenecyclobutane acids carry out a liquid-phase cyclopentadiene acrylic acid to Allen in the autoclave in accordance with the terms of the prototype method. Process conditions and results of the synthesis are given in the table.

Examples 4, 5, 6, 8. Obtaining esters methylenecyclobutane acids.

The process is carried out analogously to examples of 1.3 with the use of esters of acrylic and methacrylic acids. The modes and the results of the synthesis of esters methylenecyclobutane acids given in the table.

Example 7*(comparative). Obtaining esters methylenecyclobutane acids.

Obtaining esters IU krylovii acid. Process conditions and results of the synthesis are given in the table.

Examples 9, 10, 13. Getting NITRILES methylenecyclobutane acids.

The method is carried out analogously to examples 1, 3, using respectively the acrylic and Methacrylonitrile. Process conditions and results of the synthesis are given in the table.

Examples 11*, 12*(comparative). Getting NITRILES methylenecyclobutane acids.

Getting NITRILES methylenecyclobutane acids carried out analogously to example 2*using Acrylonitrile instead of acrylic acid in the liquid phase. Process conditions and results are shown in table.

As can be seen from the data given in the table, in accordance with the present invention, the performance of the process on target products more than 10 times the performance of the prototype method.

In addition to this performance, installation, increases the yield of the target products due to the increased selectivity of the cycloaddition process and recyclization raw material that ensures the effectiveness of the process. In addition, simplified technology of obtaining functionally samwich products.

The method of obtaining functionally substituted methylenecyclobutane, in accordance with the present invention, can be carried out on serial industrial plants petrochemical plants without significant capital investments. Technology of production of target products more simple, convenient and economical than the method prototype.

1. The method of obtaining functionally substituted methylenecyclobutane by interaction Allen derived from ethylene, containing the group-COOH or-COOR, or-CN, at elevated temperature, followed by separation of the reaction products and rectifying the selection of the target product, wherein the source is Allen's use allinaday gas containing Allen 10 to 80%, as derived ethylene, containing the group - COOR, use alkalemia esters with R = C1-C4the process is carried out in the vapor phase at temperatures above 350°C and pressures of 0.1-1.0 MPa to conversion Allen is not above 60%, at the exit of the reactor, the reaction products quenched and separated by distillation, the desired product away as a trademark, unreacted Allen and derived ethylene return in the process.

2. The method according to p. 1, characterized in that The process is carried out preferably at 400-550°C and 0.3-0.6 MPa.

4. The method according to p. 1, characterized in that alkilany ether - SOOS4- butyl ether radicals of normal, ISO - or tertiary structure.

 

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