PROCESS FOR PREPARING DIAZOMETHANE DERIVATIVE

Abstract: A crystalline diazomethane derivative of the formula: wherein R₁ and R₂ are, the same or different, a substituted or unsubstituted aromatic group is prepared by a process comprising concentrating and drying a solution of the diazomethane derivative in an organic solvent under re­ duced pressure at a temperature not higher than 30°C while applying shearing force on a viscous cake.

Description: PROCESS FOR PREPARING DIAZOMETHANE DERIVATIVE F T-bD OF THE INVENTION The present invention relates te 2 process for preparing 2 diazomethane derivative. BACKGROUND OF THE INVENTION A diazomethane derivative is known to be useful as a cc:rpound providing a protective group for a carboxylic group of an organic compound. The diazomethane derivative is an easily decompo saLe con pound as apparent from the facts that diazomethane is exD8osive, diphenyldiazomethane decomposes to form ketazine so that its purity decreases to 75 when it is kept at a rcom temperature for 2 days (see Organic Synthesis Collective Volume III, page 532). Therefore, the diazomethane derivatives are stored, transported and used in the form of a solution in z solvent used in the production step, and they have not been crystallized in a commercial scale. It is commercially disadvantageous to store, transport and handle the diazomethane derivatives in the fort of a solution. Further, when the solvent used in the production step is different from that used in the end application of the diazomethane derivative, the solution in the former solvent as such cannot be used in the end application. As the diazomethane derivatives are used in an increasing amount so that it is highly required to store it for a longer period of time, a safe and general stock form and production manner of the diazomethane derivatives are eagerly desired. SUMMARY OF THE INVENTION One object of the present invention is to provide a process for preparing a stable crystalline diazomethane derivative with high purity in a high yield. Another object of the present invention is to provide a process for preparing a crystalline diazomethane derivative, all the steps of which may be carried out in one equipment. DETAILED DESCRIPTION OF THE INVENTION The decomposition properties of crystal and solutions in methylene chloride of 1,11-diphenyldiazomethane (DD) have been studied at OOC to obtain the results as shown in Table 1. Table 1 EMI3.1 <tb> Experi- <SEP> DDM <SEP> Decomposition <SEP> Percentage <SEP> of <SEP> DDM <tb> I <SEP> ment <SEP> <tb> No. <SEP> Cony. <SEP> State <SEP> 5 <SEP> 10 <SEP> 20 <tb> <SEP> State <SEP> days <SEP> days <SEP> days <SEP> days <tb> <SEP> 1 <SEP> 20 <SEP> <SEP> Solution <SEP> 17.1 <SEP> 19.0 <SEP> 29.0 <SEP> 50.2 <tb> <SEP> 2 <SEP> 30 <SEP> Solution <SEP> 3.0 <SEP> 5.6 <SEP> 15.8 <SEP> 48.0 <tb> <SEP> 3 <SEP> 50 <SEP> Solution <SEP> 1.5 <SEP> 2.0 <SEP> t.9 <SEP> <SEP> 30.5 <tb> <SEP> 4 <SEP> 70 <SEP> Slurry <SEP> 0.9 <SEP> 1.8 <SEP> 3. <SEP> 1h.2 <tb> <SEP> 5 <SEP> 90 <SEP> Slurry <SEP> 0.2 <SEP> 0.2 <SEP> 0.h <SEP> 1.2 <tb> <SEP> 6 <SEP> 100 <SEP> Crystal <SEP> 0.1 <SEP> 0.2 <SEP> 0.3 <SEP> 1.1 <tb> According to the results, as the concentration of DDX in the solution increases, the stability increases. The slurs; which contains crystal of DDM -is more stable than the solution and the crystalline DDM which contains no solvent is most stable. Decomposability of DDM due to heat history and stability against friction or impact also have been studied. With the use of DDM having purity of 99.9 %, decomposability at various temperatures has been examined. The results are shown in Table 2. Table 2 EMI4.1 <tb> Storage <SEP> Decomposition <SEP> Percentage <SEP> of <SEP> DDM <tb> temperature <tb> ("c) <SEP> 2 <SEP> 10 <SEP> 20 <SEP> 50 <SEP> 100 <tb> <SEP> hrs. <SEP> hrs. <SEP> hrs. <SEP> hrs. <SEP> hrs. <tb> -25 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> 0 <SEP> O <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> 10 <SEP> 0.1 <SEP> 0.1 <SEP> 0.1 <SEP> 0.2 <SEP> 0.2 <tb> <SEP> 20 <SEP> 0.2 <SEP> 0.6 <SEP> 0.7 <SEP> 1.0 <SEP> 2.5 <tb> <SEP> 25 <SEP> 0.4 <SEP> 0. <SEP> 1.8 <SEP> - <SEP> 4.4 <SEP> 8.6 <tb> <SEP> 30 <SEP> (melt) <SEP> 1.4 <SEP> 6.8 <SEP> 13.2 <SEP> 29.8 <SEP> 50.7 <tb> <SEP> 40 <SEP> (melt) <SEP> 4.0 <SEP> <SEP> 17.7 <SEP> 32.2 <SEP> 62.2 <SEP> 85.7 <tb> <SEP> 50 <SEP> (melt) <SEP> 5.5 <SEP> 39.0 <SEP> 90.5 <SEP> 100 <SEP> 100 <tb> As understood from the results of Table 2, DDM. does not substantially decompose at a temperature lower than 50C, but gradually starts to decompose at a temperature higher than 100C, and about 5 % decomposes at 250C after 50 hours and 5 % or more at 300C after only several hours. Since the melting point of DDM is about 29-310C, it melts at a temperature higher than 290C and it quickly decomposes in a melt state. This is further confirmed by the following experiments. DDM with purity of 99.9 % is once molten at 300C and kept in a supercooling state while maintaining the melt state at various temperatures. The decomposition percentages are shown in Table 3. Table ; EMI5.1 <tb> Storage <SEP> Decomposition <SEP> percentage <tb> Conditions <tb> <SEP> 2 <SEP> 10 <SEP> 20 <SEP> 50 <SEP> 100 <tb> Tep. <SEP> State <SEP> hrs. <SEP> hrs. <SEP> hrs. <SEP> hrs. <SEP> hrs. <tb> <SEP> 0 <SEP> 0 <tb> <SEP> 50C <SEP> Crystal <SEP> O <SEP> 0 <SEP> 0 <SEP> <SEP> O <SEP> O <SEP> <tb> <SEP> Melt <SEP> 0.3 <SEP> 1.3 <SEP> 2.5 <SEP> 6.2 <SEP> 12.0 <tb> 15 C <SEP> Crystal <SEP> 0.1 <SEP> 0.1 <SEP> 0.2 <SEP> 0.S <SEP> 0.6 <tb> <SEP> Melt <SEP> 0.3 <SEP> 1.h <SEP> 2.6 <SEP> 6.5 <SEP> 13.1 <tb> 250C <SEP> Crystal <SEP> 0.4 <SEP> 0.9 <SEP> 1.8 <SEP> 4.4 <SEP> <SEP> 8.6 <tb> <SEP> Melt <SEP> 0.9 <SEP> h..3 <SEP> 8.3 <SEP> 19.5 <SEP> 35.4 <SEP> <tb> As is apparent from the results of Table 3, the decomposition rate in the melt state is far greater than that in the crystalline state at the same temperature. From the analysis of these data according to reaction kinetics, it has been found that the decomposition reaction is a first order reaction and its activation energies in the crystalline and melt states are 72.7 kcal/mol and 19.4 keal/m.ol, respectively. Since an activation energy of a very easily decomposable organic peroxide is about 20-30 keal/mol, DDM in the melt sate decomposes as easily as or more easily than the organic peroxide. To examine the stability of DDM against friction and impact, the same pure DDM as used in the above experiment (purity 99.9 p) was subjected to drop hammer test, friction test (according to JIS K 4810-1797), ignition test (according to the Crupp method), steel pipe test, pressure container test (cf. D.C. Noelor et al: Ind. Eng. Chin. 5618 (1964)). The results are as follows: Drop hammer test: 8th class Friction test: 7th class Ignition point: 136-1390C Steel pipe test: 6th class Pressure container test: burst with No. 7 orifice From all the above results, it is concluded that DDM is comparatively stable against friction and impact so that it does not quickly decompose and excde, it gradually decomposes as heated but quickly decomposes in the melt state. Further, the solution of DDE becomes very viscous as it is crystallized and dried so that it easily adheres on a equipment for treatment and prevents heat transfer or decreases drying efficiency, which results in low yield. Thus, the present invention relates to a stable crystalline diazomethane derivative and a safe process for preparing a diazomethane derivative. By the crystallization of the diazomethane derivatives, its application fields will be broadened. Accordingly, the present invention provides a process for preparing a crystalline diazomethane derivative of the formula: EMI7.1 wherein R1 and R2 are, the same or different, a substituted or unsubstituted aromatic group, which comprises concentrating and drying a solution of the diazomethane derivative in an organic solvent under reduced pressure at a tetnpera- ture not higher than > 0 C while applying shearing force on 2 viscous cake. Specific examples of the diazomethane derivative (I) are diphenyldiazo:nethane, p-n.ethyldiphenyldiazcmethane, p-chlorodiphenyldiazomethane, p-nitrodiphenyldiazomethane, p,p'-dichloroliphenyIdiazomethane and the like. Specific examples of the organic solvent are methylene chloride, 1,2-dichloroethane, chloroform, ethyl acetate, ethyl ether, petroleum ether, n-hexane, n-heptane, benzene, and the like. The solution to be treated by the process of the present invention may be a solution obtained in the production step of the diazomethane derivative in the -above solvent or a solution made by dissolving the crystalline diazomethane derivative in the above solvent. Since it is preferable to carry out the concentration and drying of the solution as quickly as possible for effective preparation of the diazomethane derivative according to the present invention, the solvent has as low boiling point as possible and no flammability. Among the solvents, methylene chloride is most preferred. The diazomethane derivative (I) may be prepared by a per se conventional method, for example, comprising oxidizing a corresponding hydrazone derivative with a suitable oxidizing agent (e.g., manganese dioxide, mercury oxide, silver oxide, peracetic acid, hydrogen peroxide, etc.). Particularly, electrolytic manganese dioxide is preferred since it gives the highly pure diazomethane derivative in a high yield. The concentration and drying of the solution of the diazomethane derivative are carried out under reduced pressure at a temperature not higher than 300 C, preferably not higher than 250C and not lower than -250C. At a temperature higher than 3O0C, the crystalline diazomethane derivative melts and quickly decomposes. This leads to the deterioration of the quality and yield of the product. The pressure depends on other conditions such as the kind of the solvent, the concentration of the solution, the temperature, etc. As the concentration and drying of the solution proceed, the solution becomes a very viscous cake and tends to adhere on a stirrer or other equipments. However, when the viscous cake of the diazomethane derivative is further dried with applying the shearing force thereon, the cake gradually loses adhesivity and finally powdered. Although the present process can be carried out in one step, the solution may be concentrated to form a slurry in one equipment and then dried by means of a dryer which can apply the shearing force. Examples of an equipment which can apply the shearing force on its content are a dryer with a selfcontained vertical type screw or ribbon, a vacuum rotary dryer, a Uninix dryer, and the like. Among them, the most preferred is the dryer with the self-contained vertical type screw or ribbon, for example, a Nauta type dryer, since only a s-211 zmount of the cake adheres to this type of dryer and the yield of the powder is increases. The present invention will be hereinafter explained further in detail by following examples. Example 1 A 50 ^ solution of diphenyldiazomethane (20 kg, purity 99.0 %) in methylene chloride (20 kg) was charged in a Wauta type 50 1 dryer (a vacuum dryer consisting of a reverse cone shaped vessel equipped with a rotating and orbiting screw type agitator and a jacket. Rotational speed 70 RPM. Orbiting speed: 2.6 RPM). The internal pressure was gradually reduced to 10 Torr while keeping the jacket temperature between -7 and -20C to obtain diphenyldiazomethane (19 kg) with purity of 98.9 Qp. Example 2 A 50 % solution of diphenyldiazomethane (2 kg, purity 99.0 %) in methylene chloride (2 kg) was charged in a 10 1 vacuum rotary dryer (consisting of an agitator having four lines of blades (on each line, 5 flat blades are obliquely attached) and a jacket. Rotational speed: 8 Rum). The internal pressure was gradually reduced to 10 Tcrr while keeping the jacket temperature between -5 and OOC to obtain diphenyldiazomethane (1.6 kg) with purity of 8.8 -. Example 3 To a glass-lined 100 1 reactor, methylene chloride (22 kg) was charged and benzophenone hydrazone (2 k±) was mixed. To the mixture, electrolytic manganese dioxide containing 91.0 % of effective oxygen (39 kg) was added at a temperature of 20 to 250C over 2 hours and then stirred at the same temperature for 2 hours. Then, the reaction mixture was filtered and the filter cake was washed with methylene chloride. The washing solvent was combine with the filtrate. The purity of the product in the combined solution was 30 %. The solution was charged in the same Nauta type dryer as used in Example 1. The internal pressure was gradually reduced to 10 Torr while keeping the jacket temperature between 10 and 1500 (the internal temperature 5 to 150C) to obtain diphenyldiazomethane (26 kg) having purity of 99.0 °. Yield 91 ds,

Claims: CLAIMS: 1. A process for preparing a crystalline diazomethane derivative of the formula: EMI11.1 wherein R1 and R2 are, the same or different, a substituted or unsubstituted aromatic group, which comprises concentrating and drying a solution of the diazomethane derivative in an organic solvent under reduced pressure at a temperature not higher than 300C while applying shearing force on a viscous cake. 2. A process according to claim 1, wherein the organic solvent is one selected from the group consisting of methylene chloride, 1,2-dichloroethane, chloroform, ethyl acetate, ethyl ether, petroleum ether, n-hexane, n-heptane and benzene. 3. A process according to claim 2, wherein the organic solvent is methylene chloride. 4. A process according to any one of the preceding claims, wherein the temperature is from -25 to +250C. 5. A process for preparing a crystalline diazomethane derivative of the formula: EMI12.1 wherein R1 and R2 are, the same or different, a substituted or unsubstituted aromatic group, which comprises concentrating and drying a solution of the diazomethane derivative in an organic solvent under sub-atmospheric pressure at a temperature not higher than 300C until a cake of partially solidified derivative forms, and thereafter continuing concentration and drying of the cake under sub-atmospheric pressure at a temperature not higher than 300C while applying shearing force to the cake.

Inventors: HIRAYAMA, YOSHIHIKO, KOHNO, YUKITOMO, SAIJO, SHIGEYA, SAKAI, TAMIO, SAKAMOTO, SUKEHIKO, SHIRAISHI, YOSHIHISA
Applicants: TAOKA CHEMICAL CO., LTD
Application year: 1985
Main classification: C07C113
IPC codes: C07C67, C07C241, C07C245