• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Process for the production of N-methylcarbamates: (wherein RO- is the radical of a substituted phenol or of a naphthol), wherein: - in a first reaction step methylamine and diphenyl carbonate are reacted with each other, operating in the liquid phase and as a continuous process, in order to form phenol and phenyl-N-methylurethane; - in a second reaction step phenyl-N-methylurethane, within the related reaction mixture outcoming from the first step, is thermally continuously decomposed, to yield a gaseous stream containing methyl isocyanate, from which the components different to methyl isocyanate are condensed off; - in a third step the methyl isocyanate stream, outcoming from the second step. after a possible preliminary condensation, is continuously fed and contacted with a solution of a substituted phenol or of a naphthol in an inert organic solvent, containing a basic catalyst, to form N-methylcarbamate (I); N-methylcarbamate (I) is finally recovered from the reaction mixture outcoming from the third step.
    公开号:SU1433410A3
    申请号:SU853995137
    申请日:1985-12-20
    公开日:1988-10-23
    发明作者:Риветти Франко；Мидзиа Франко；Гароне Гвидо；Романо Уго
    申请人:Эникем Синтези,С.П.А. (Фирма)；
    IPC主号:
    专利说明:

     (J
    one
    14334
    The invention relates to an improved process for the preparation of N-methyl carbamates, carried out in continuous mode. N-methyl carbamates are valuable products, active phyto-pharmacological prescription drugs, for example, compounds such as 2,3-dihydro-2 , 2-dimethylphenzofuran-7-yl-K-methylcarbamate (iz-Local called carbofuran),) -naphthyl-N-methylcarbamate (known as carbaryl)
    I The purpose of the invention is to simplify the technology and increase the safety of the process.
     According to the invention, N + methylcarbamates of the formula
     OR
    s-o
    -Mvr r "w .. (O
    IN-SNZ
    102
    from the liquid stream of phenol and phenyl-N-methylurethane, the latter being recycled to the thermal decomposition stage.
    3 stage.
    Methyl isocyanate stream, coming from the old stage, is continuously fed into the third reactor and brought into contact with a solution of substituted phenol or naphthol in an inert organic solvent at room temperature of 0–50 ° C in the presence of an amine type catalyst to produce N- methyl carbamate of the indicated formula; finally, the N-methyl carbamate is separated from the reaction mixture leaving the third stage.
    1-stage.
    In the first stage, diphenyl carbonate and methylamine react with each other to form phenyl-L-methylurethane and phenol in accordance with the following reaction scheme:
     R is phenyl, substituted by keel, dimethylamino, thio-C, 1: yl, 2,3-dihydro-2,2-dimethyl-7-ben-ben: 1 furanyl, 2, 2-dimethyl-1,3 benzodi-C1XI, naphthyl . I The process is carried out in 3 stages.
    1-stage.
    Diphenyl carbonate and methylamine are continuously fed to the first reactor together with a recirculating liquid stream consisting of the reaction mixture leaving the said first reactor, and the reaction is carried out in phase at the molar ratio of methylamine to lyphenylcarbonate reacting 0.8-1: 1, and at 50 ° C to form phenyl-N-methylurethane and phenol.
    2-stage.
    The second reactor is continuously supplied with a reaction mixture coming from the first stage and a recirculating stream containing phenyl-N-methylurethane conducting reaction in a boiling liquid phase at 210 ° C and at atmospheric pressure with the system to partially decompose the phenyl-N- methylurethane (decomposition degree 5-6%) to phenol and methyl isocyanate and create a gaseous stream containing phenol, methyl isocyanate and unreacted phenyl-K-methyl urethane, and the gaseous stream is condensed to separate the gaseous stream of methyl isozoic
    / WH-SNZ
     -C 0+ PhOH
    OPh

    where Ph is a phenyl radical.
    Temperature below 20 ° C dramatically reduces the reaction rate. Temperatures above 80 ° C are undesirable since the secondary reaction leading to the formation of N, N -dimethylurea, is favored. in accordance with the following reaction scheme:
    ZCHjUHz
    Insnz
    C - O -t- ZPhOH
    SOGNS
    where Ph is a phenyl radical.
    Such a reaction proceeds to a noticeable degree, especially at a temperature higher than 100 C.
    In practice, a continuous stream of methylamine and a continuous stream of diphenyl carbonate dissolved in the recirculating liquid mixture can be fed to the first stage reactor.
    The reactor of the first stage can be a moving reactor, which is continuously fed to the reactor.
    reagents and recirculating fluid and from which the reaction mixture is continuously withdrawn. Alternatively, an elongated reactor may be used, for example a tubular reactor, at one end of which a continuous supply of reagent and recirculating fluid is carried out, and at the other end the reaction mixture is withdrawn.
    When operating under the specified conditions, the reaction is completed or mostly completed within 15-60 minutes in the absence of substances that have a catalytic effect on the indicated reaction.
    As a rule, when operating under these conditions and with stoichiometric or close to stoichiometric amounts of reagents, diphenyl carbonate conversion is usually 98% or higher with selectivity to phenyl-N-methylurethane, usually above 99%, calculated on the amount of diphenylcarbonyl converted. Bonat, where all percentages are given in molar terms.
    The reaction mixture withdrawn from the reactor of the first stage is partially recycled, and the remaining amount is continuously fed to the reactor of the second stage.
    2-stage.
    In the second stage, phenyl-L-methylurethane is thermally decomposed into methylis, cyanate and phenol in accordance with the following reaction scheme:
    Orb
    from o -
    IN-SNZ
    CHj-N-C-O + PhOH
    where Ph is a phenyl radical.
    A liquid stream consisting of reaction products from the first stage and recirculating liquid phenyl-N-methyl yrethane is continuously fed to the reactor of the second stage, and the reaction is performed in a boiling liquid phase at 210 ° C and atmospheric pressure in the absence of substances having a catalytic effect on the reaction decomposition in order to partially (10-90%) decompose phenyl-N-methylurethane into phenol and methyl isocyanate. Under these conditions, in the second-stage reactor 0
    five
    five
    0
    five
    0
    five
    0
    five
    The din creates a gaseous stream containing methyl phenol phenol and unconverted phenyl-L-methylurethane. This stream is cooled, for example, to a temperature in the order of 80-100 ° C so as to separate the gaseous stream of methyl isocyanate from the liquid stream of phenol and phenyl-L-methylurethane. The liquid stream thus obtained is distilled off in such a way that it is frequent. Separately or completely separate the phenol as the main product from the tail product consisting of or containing phenyl L-methylurethane, and this tail product is recycled to the second stage reactor.
    The process of the second stage is carried out at 210 ° C, at atmospheric pressure, with an average residence time in the reaction zone (which is calculated as the ratio of the space velocity of the feed stream to the free volume of the reactor) 0.5-3 hours. In addition, a sufficient amount of water is supplied to the reactor. : The amount of heat in order to create a volumetric rate (in weight terms) of the evaporated substance is 1.5-11 times higher than the volumetric rate of the reactants supplied. Under these conditions, conversion of phenyl-K-methylurethane is achieved over a passage of about 65-85% based on the feed amount and a gaseous stream is formed in the reactor containing 9-22% by weight of unconverted phenyl-N-methylurethane, 63-71 wt. .% phenol and
    15-20 Mac.jS methyl isocyanate.
    I
    The reactor in which the second stage is carried out is a tubular reactor, at the top of which a reflux condenser is mounted, preceded or not by distillation plates, or a section with a nozzle.
    When operating under the specified conditions, complete or almost complete conversion of phenyl-N-methylurethane is achieved, with selectivity for methyl isocyanate above 98 mol.%.
    3 stage.
    In the third stage of the process, methyl isocyanate, coming out as a gaseous stream from the second stage, reacts, sometimes after condensation, with a substituted phenol or naphthol dissolved in an organic solvent, in accordance with the following reaction scheme:
    CH3-N-C.0-1-ROHOR
    CH-CH3
     R represents the radical ea m4 | Valuable phenol or naphthol.
    I Examples of compounds of the formula R OH HE include: 1-naphthol; 2-naphthol; 2,3-dihydro-2,2-dinetylbenzofuran-2,2-dimethyl-1,3-benzodiox-c (l-4-ol; 3,5-xylenol; 3,4-xylanol; 2-isopropylphenol ; 2- (ethylthiomethyl) -phenol; 2-cresol; 3-isopro-5-methylphenol: 4-methylthio-3, 5-di-methylphenol; 4-dimethylamino-3 methyl-.
    Methyl isocyanate, excreted in the thirth stage, is continuously supplied and in contact with a solution of compound K) H in an inert organic p; 1 solvent, also containing an amine cat.
    I
    Organic solvents are aromatic carbon, such as benzene, toluene, k; ilol and cumene, such ketones as adheton, methyl ethyl ketone and methyl isobutyl ketone, such complex esters as e-ylate, methyl acetate, dimethyl carbonate and diethyl carbonate , chlorinated aliphatic hydrocarbons, such as chloroform, methylene chloride, carbon tetrachloride and di.chloroethane; ethers such as dithyl ether or tetrahydrofuran. Usually the coa: the concentration of the compound in the corresponding 2-nd organic solution is in the range of 5 wt.%.
     Specific examples of the catalysts used in this process include triztilamine, diisopropyl ethylamine, pyridine, 4-dimerschroic, redin, N-methylimidazole.
    Preferred catalysts are tertiary amines.
    The amount of catalyst used in the third stage of the reaction can usually vary from 0.001 to Ojl mol per mol of ROH compound.
    In addition, the third stage reaction is carried out at an equimolar or close to equimolar ratio between the ROH compound and methyl isocyanate, especially at ratios of 1-1 to 1: 1,
    The third stage of the process can be carried out using a large number of reactors arranged in parallel, each of the reactors containing a solution of the compound ROH, in a selected organic solvent, in addition to the catalyst. In the case of a methyl isocyanate stream, which can be converted to a liquid state, it is continuously fed to the first reactor until the desired molar ratio between the reactants is reached, then the methyl isocyanate stream
    diverted to the second reactor.
    After the completion of the supply of methyl isocyanate, the first reactor was maintained under the reaction conditions for 0.5-8 hours to complete the reaction, and finally the N-methylcarbamate was separated from the reaction mixture.
    This cycle is repeated in the second reactor, etc.
    The residence time of the reagents 0.5-8 hours
    The third stage is carried out in stirred reactors using a technological scheme with parallel arrangement of reactors. In continuous operation, it is preferable to use a series of continuous reactors arranged in series, or use an elongated tubular reactor, at one end of which reactants are continuously fed, and the reaction mixture is continuously withdrawn from the other end.
    When operating under these conditions, N-methylcarbamate e is usually obtained.
    output, as a rule, above 98 mol.% in the calculation of the submitted reagents. N-methylcarbamate is separated from the reaction mixture leaving the third stage, by known methods,
    for example, by concentration, crystallization, filtration, drying, or by any combination of these operations. According to a preferred embodiment, the solvent is for
    the third stage is chosen in such a way as to facilitate the precipitation of N-methylcarbamate in order to facilitate its separation from the reaction mixture, which, therefore, can
    directly recycle after first dissolving the ROH compound.
    The N-methylcarbamate thus isolated can be purified 7
    by recrystallization from an inert solvent as a result of dissolving the substance at a high temperature in a suitable solvent and forcibly subsequent precipitation as a result of cooling the solution. It is best of all that the temperature at which the solution of the crude N-methyl carbonate is heated is maintained at a lower value than that which causes the destruction of such a compound, such a temperature usually has a lower value.
    L-metascarbamates are prepared so that at any given time the amount of free highly toxic methyl isocyanate is kept at an extremely low value, which eliminates or at least greatly simplifies the problems associated with using the compound, if necessary, to store it.
    The proposed method makes it possible to obtain N-methylcarbamates with high yields and selectivity by a simple and cheap method. In addition, the continuous operation demonstrates, with respect to the periodic mode, a number of advantages, consisting in higher productivity per unit volume of equipment, greater uniformity of the characteristics of the final products and the possibility of automating the technological process.
    The advantage of this method is also to conduct the process at the 1st stage in a recycle stream, without using an organic solvent, which eliminates the stage of subsequent distillation and contamination of the streams of the target products. The absence of an organic solvent eliminates the ingress of foreign substances into the reaction mass, resulting in a reaction mixture that can be directly processed in step 2.
    When carrying out the process, as shown for stage 2, the release of methyl isocyanate stream is regular and constant and there is no need for intermediate storage of this hazardous chemical product.
    In addition, the proposed method provides greater process flexibility, has the ability to obtain

    4334108
    a large number of various N-methylcarbamate,
      . Example 1 In the drawing, the index Р-1 designates the reactor of the first stage, equipped with a bash mixer and operating at a pressure of 0.98 kg / cm. Reactor R-1 through line 1 is continuously fed at a flow rate of 1.3 kg / h.
    JQ (42 mol / h) is a stream of methylamine, and through line 2 it is supplied at a rate of 22.5 kg / h. liquid stream containing 40 wt.% diphenyl carbonate. Flow through line 2 is obtained as a result. 9.0 kg / h delivery
    15 (mol / h) of diphenyl carbonate through line 3 and 13.5 kg / h of effluent from reactor R-1, through line 4. The residence time in reactor R-1 is 0.5 hours and in line 5 is discharged with flow
    2Q 23.8 kg / hr stream having the following composition, wt.%: Phenol 38; phenyl-K-methylurethane 61; diphenyl carbonate 0.8. The output of N-methylurethane per diphenyl carbonate 99%.
    25 I
    This stream is partially (kg / h)
    recycle in the reactor through line 4, and the remainder (10.3 kg / h) is -. The flow is through line 6, which is fed to the second stage reactor P-2 together with the flow coming from the bottom of column C-1, through line 7.
    The specified bottom stream from column C-1 has a volumetric rate of 2.3 kg / h and the following composition, wt.%: Phenol 39;
    35 phenyl-N-methylurethane 61. Therefore, the resulting stream fed to the reactor R-2 through line 8, has a volumetric rate of 12.6 kg / h and the following composition, wt.%: Phenol 38, phenyl-K-methylcarbamate 61 and diphenyl carbonate 0.7.
    thirty
    The second stage reactor P-2 operates under the following conditions: a temperature of 210 ° C, atmospheric pressure and a residence time in the reactor for 2 hours. Under these conditions, pyrolysis of phenyl-N-methylurethane takes place and a gaseous stream is formed, which cools down. 100 C In the subsequent reflux condenser and get the liquid phase of the following composition, wt.%: Phenol 86.2 and a flash of n-methyl methyl 13.8. This liquid phase is partially recycled to the second stage reactor R-2 (recirculation coefficient 10), and the remainder constitutes flow through line 9, which is fed at a volumetric rate of 10.1 kg / h to the C-1 distilling column.
    91
    Distillation column C-1 operates at a pressure measured at the top of the column, equal to 10 mm Hg. at the temperature of the upper part of the block at 78 ° C and at the temperature of the lower part of the column at 108 ° C. In these conditions, phenol is separated from the top of the column C-1 with a speed of 7.8 kg / h. | from the bottom of the column, an almost equimolar flow of phenol and phenyl-K-methylurethane (corresponding to I BfJHHo 39 and -51 wt.%), which is recycled to the pyrolysis reactor Pf2 via line 7 with a volumetric velocity of JTbro 2.3 kg / h
    ; From the lower part of the pyrolysis reactor, high-level by-products are also periodically effected, which are about 5 in very small quantities B | IX (less than 0.03 kg / h).
    The methyl isocyanate, which is formed during pyrolysis in the reactor of the second stage P-2, does not become liquid with c-iroHHHe at the temperature at which the pyrolysis products are partially concentrated and expelled along line 11 at a rate of kg / h. The output of methyl isocyanate in the calculation of diphenylcarbonate 98,1%. This stream is reduced in heat exchanger E-1 and fed to the P-Over reactor, which is preloaded, in kg: 2 3-dihydro-2,2-dimethyl-7-benzofura-NF1 28.6; toluene 86; triethylamine 0.18 (catalyst). The secondary phenol is withdrawn via line 12.
    The methyl isocyanate stream is fed to the P-Za reactor for 4 hours at
    and atmospheric pressure. After the end of this period, the methyl isocyte flux
     R-Zv is discharged into the reactor, works in parallel with the P-Za reactor and -containing the same initial load of reagents.
    After the supply of methyl isocyanate to the reactor, P-Over, the contents of the reactor are held for 2 hours with stirring and at the indicated temperature. Then the contents of the reactor in P-Za or P-Zv are discharged through line 13 or 14 and filtered in order to separate the precipitated 2,3-dihydro-2,2-dimethylbenzene-furan-7-yl-H-Methylcarbamate, which is washed with toluene and dried at 80 ° C and a residual pressure of 10 mm Hg.
    Uterine fluids containing an excess of 2,3-dihydro-2,2-dimethyl-7-ben10
    0
    34
    j
    five
    (
    thirty
    five
    five
    0
    five
    1010
    zofuranol, dissolved 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-H-methylcarbemate (1-2 wt.%) and the catalyst, can be completely regenerated (or by withdrawing a small amount) with the purpose of obtaining a solution that is loaded into a third stage reactor.
    The total amount of 2, 3-dihydro-2,2-dimethyl-benzofuran-7-yl-y-methylcarbamate (carbofuran) thus obtained was 36.0 kg at a yield of 1 kg of the desired desired product per 1 kg of diphenyl carbonate (96.8 mol.%).
    This cycle is repeated using the P-Sv reactor; results are obtained that are close to those obtained in the P-Za reactor.
    Example 2. The process is carried out according to the procedure described in example 1, loading the following products into the reactor of the third stage, kg: 1-naphthol 25.1; toluene 75; triethylamine O, 18 (catalyst).
    In one cycle, 32.5 kg of 1-naphthyl-L-methylcarbamate (carbaryl) are obtained with a yield of 96 mol.% Calculated as diphenyl carbonate.
    Example 3. The process is carried out. according to the procedure described in example 1, loading the following substances into the reactor of the third stage, kg: 2-isopropoxyphenol 26.5; toluene 80; triztilamine 0.18 (catalyst).
    In one cycle, 34 kg of 2-isopropoxyphenyl-L-methylcarbamate (Proxur) are obtained with a yield of 97 mol.% Calculated as diphenylcarbonate. I
    Example 4. When working according to the procedure described in example 1, loading the following compounds into the reactor of the third stage: 4-dimethylamino-3-methylphenol; 3,5-xylenol; 3,4-xylenol; 2,2-dimethyl-1,3-benzodioxol-4-ol; 4-methylthio-3, 5-dimethylphenol; 3-isopropyl-5-methylphenol; 2-cresol; 2-isopropylphenol; The following carbamates are obtained from 2- (ethylthiomethyl) -phenol: 4-dimethylamino-3-methylphenyl-N-methylcarbamate (aminocarb); 3,5-xylyl-N- -methylcarbamate (HMMS); 3,4-xilyl-N-methylcarbamate (MRMS); 2,2-dime-TSH1-1,3-benzodioxol-4-yl-methylcarbamate (Bendiocarb); 4-methylthio-3, 5-xylyl-N-methylcarbamate (methiocarb); 3-isopropyl-5-methylphenyl-N-methylcarbamate (promecarb); 2-isopropylphenide-N-methylcarbamate (isoprocarb); 2-tolyl-N-methylcarbamate (MTMS); 2- (ethylthiomethyl) -fe1 Shl-L-methylcarbamate (ethiofencarb).
    The yield of the target products in the calculation of diphenylcarbamate fed to the first stage, 95-98%.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining N-methyl carbamates of the general formula
    / OR
    with “o
    And-SNZ
    where R is phenyl, substituted with C, -Cj-alkyl, dimethylamino, thio- -C (-C-alkyl, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl, 2,2- dimethyl-1,3-benzodioxy, naphthyl,
    using the interaction of the corresponding substituted phenol or naphthol with methyl isocyanate in an inert organic solvent at room temperature in the presence of an amine-type catalyst with separation of the target product, which is characterized by the fact that, in order to simplify the process and increase the safety of the process
    Q
    five
    Q 5
    Q
    phenyl carbonate is reacted with methylamine at 50 ° C with a molar ratio of reagents of 0.8 - 1: 1 in the liquid phase in the presence of a diluent - recycle liquid reaction mass obtained in this case, with a continuous supply of methylamine together with 40% diphenyl carbonate in recirculating solution, followed by thermal decomposition of the directly obtained reaction mass and the recycling liquid stream containing enyl-N-methylurethane, continuously fed to the second reactor, while boiling the reaction mixture at a temperature and atmospheric pressure to the extent of phenyl-N-methylurethane 5-6% decomposition into phenol and methyl isocyanate to form a gaseous stream containing phenol, methyl isocyanate and unreacted phenyl-N-methylurethane, cooled to 100 ° C separating the gaseous methyl isocyanate stream from the liquid phenol and phenyl-N-methylurethane stream, rectifying the latter and recycling the phenyl-N-methylurethane thus obtained to a thermal decomposition stage, and the gaseous methyl isocyanate stream is continuously fed rety reactor for reaction with the appropriate substituted phenol or naphthol.
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    同族专利:
    公开号 | 公开日
    AT58722T|1990-12-15|
    CN1004353B|1989-05-31|
    US4659845A|1987-04-21|
    KR860006435A|1986-09-11|
    IL75080D0|1985-09-29|
    EP0190466B1|1990-11-28|
    AU5121585A|1986-08-14|
    ZA859406B|1986-08-27|
    BR8502202A|1986-04-15|
    IL75080A|1989-07-31|
    JPS61183257A|1986-08-15|
    IT1183332B|1987-10-22|
    IT8519453D0|1985-02-08|
    JPH0617356B2|1994-03-09|
    AU580823B2|1989-02-02|
    DE3580749D1|1991-01-10|
    MX168252B|1993-05-14|
    CA1249594A|1989-01-31|
    EP0190466A1|1986-08-13|
    CN85109417A|1986-12-03|
    KR870000673B1|1987-04-06|
    引用文献:
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    IT1222428B|1987-07-31|1990-09-05|Enichem Sintesi|PROCESS PERFECTED FOR THE PRODUCTION OF N ALCHILCARBAMMATES|
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    法律状态:
    2007-09-20| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: MM4A Effective date: 20031221 |
    优先权:
    申请号 | 申请日 | 专利标题
    IT19453/85A|IT1183332B|1985-02-08|1985-02-08|PROCEDURE FOR THE PRODUCTION OF N-METHYL CARBAMATES|
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