• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:

    公开号:SU971097A3
    申请号:SU792760905
    申请日:1979-05-04
    公开日:1982-10-30
    发明作者:Олливье Жан；Сулумяк Ги；Сюберлюкк Жаннин
    申请人:Сосьете Насьональ Елф Акитэн /Продюксьон/(Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved method for producing alkyl mercaptans, which are widely used in organic synthesis.
    A known method of producing alkyl mercaptans, which consists in the interaction of an olefin with hydrogen sulfide under ultraviolet radiation [1].
    However, this method is characterized by a high induction reaction period and a low degree of olefin conversion.
    Closest to the proposed is a method for producing alkyl mercaptans, which consists in the photochemical interaction of an olefin and hydrogen sulfide in the presence of trialkyl or triaryl phosphite at 24 ~ 33 ° C and a pressure of 126 atm.
    The conversion of olefin in this method is $ 20-98 [2].
    A disadvantage of the known method is the use of ultraviolet radiation with a wavelength of up to 300 nm, which is due to the need for a scavenger;>
    clean the reagents and solvents from impurities absorbing in this area. In addition, due to the absorption of hydrogen sulfide and mercaptan, reaction 5 significantly slows down at small degrees of conversion and is accompanied by a side process - the addition of mercaptan at the double bond of olefin.
    The purpose of the invention is to simplify the process associated with the use of long-wave radiation.
    This goal is achieved by the fact that according to the method for producing alkyl mercaptans, the olefin is subjected to a photochemical reaction with hydrogen sulfide in the presence of phosphite and benzophenone and / or thiobenzophenone in an organic solvent at a pressure of 1 ~ 5 atm and a temperature of 0 ~ 20 ° C.
    When irradiated with light with a wavelength of 300-400 nm, benzophenone is preferably used.
    When irradiated with light with a wavelength of 25 '350-600 nm, thiobenzophenone is used.
    in the case of a light source with a wavelength range of 300-600 nm, a mixture of benzophenone and thiobenzophenone is preferably used.
    Benzophenone and / or thiobenzophenone pre-5 3 are respectfully used in an amount of 0.001-0.05 mol / h.
    As a solvent, ethylene glycol ether or aromatic or aliphatic 10 ““
    Continuation of the table | 3 | 4
    Benzophenone 0.014 together with tridecyl phosphite 0, OB 0.18 hydrocarbon, or methylal.
    The main distinguishing feature of the method is the process in the presence of benzophenone and / or thio-benzophenone in an organic solvent 15 at 0-20 ° C.
    EXAMPLES 1 * 3 · A classic pyrex photochemical reactor is used, equipped with a submersible coaxial lamp, the base 20 of the vessel being fused to provide good diffusion of gaseous hydrogen sulfide and propylene. The irradiated volume is 130 ml. The thermostatic reactor with double external ru 25 head, which operates continuously using the appropriate pressure; the gas flow rate is kept constant during the experiment and is 30 l / h for hydrogen sulfide and 28 l / h for 30 propylene. Diethylene glycol dimethyl ether is used as a solvent; the temperature at which hydrogen sulfide and propylene are saturated is 0 ° C. The concentration of the photosensitizer corresponds to the optimal profile of the intensity of the radiation absorbed in the reactor. The light source is a low-pressure reverse-emission mercury lamp with a maximum at 350 nm. The power of the light source is 8 watts. After 35 minutes, the numbers of formed sercaptans are (see table).
    Examples Initiator The amount of initiator mol / l The amount of mercaptan,• moth ή Ί 3 4 1 Benzsh ^ enon 0.014 0.12
    Tridecylphosphate 0.660 0.07
    From example 3 it is seen that the combined use of benzophenone and phosphite / leads to the production of mercaptan in an amount exceeding 2.57 times the amount of mercaptan obtained using only phosphite.
    PRI me R 4. Obtaining p-propanethiol.
    The photochemical reaction is carried out in a cylindrical pyrex reactor with a capacity of 250 ml, equipped with an immersion coaxial lamp. Cooling and mixing of the reaction mixture is carried out using an external drive, which is cooled so as to maintain a temperature of 18 ° C in the external environment. The reactor is equipped with a 8 W fluorescent lamp, with a maximum of 'at 350 nm.
    160 ml of diethylene glycol dimethyl ether (diglyme) are introduced into the reactor and the solvent is saturated under a pressure of 3 bar with a gas mixture of hydrogen sulfide and propylene. The consumption of hydrogen sulfide is 90 l / h, the consumption of propylene is 30 l / h. These costs are maintained constant throughout the process. The pulsation smoothing device located at the gas flow inlet against the torch allows maintaining a constant pressure in the reactor. The system is connected to a safety valve, which is under the backpressure of the light. An electrically operated valve that controls the level of reagents allows continuous removal of effluents formed after passing the squeezing device, which is a grate. The solvent contains 0.0055 mol of benzophenone and 0.0022 mol of triphenylphosphate per liter of solution; it is fed continuously using a metering pump with a flow rate of 350 ml / l. While the reactor is set to continuous steady state, the volume of the reaction mixture is maintained at 240 ml. In this reactor, 20.13 g of n-propylthiol and 4.04 g of dipropygium sulfide are produced continuously per hour. Therefore, the yield of mercaptan (by mass) is 83.3%. · Mercaptan is isolated by distillation after separation of the residual hydrogen sulfide and propylene, which are returned to the cycle.
    PRI me R 5 · Carry out the same operations as in example 4, introducing 120 l / h of hydrogen sulfide and 10 l / h of propylene. * * The amount of mercaptan obtained per hour is
    For example, butene-1 is creeped in the same way, 0.280 mol of butyl mercaptan is obtained.
    PRI me R 7. Perform the same operations as in example 1, except that instead of benzophenone is-20 use thiobenzophenone (5 · 10 ~ ^ mol / l); all other conditions remain unchanged. The amount of mercaptan obtained is 0.15 mol.
    A walkie-talkie, that is, as dean.
    21.5 g, yield 90%.
    ER 6. The same operations are carried out in Example 1, except that instead of propylene, 15 ER R 8 is carried out. The same one-25 'is carried out and in Example 1, then use something up to ~ instead of diethylene glycol solvent.
    The yield of mercaptan is 24%.
    PRI me R 9 · Conduct the same one-30 radio, as in example 1,
    ’. NOW
    P for an exceptionally ester, substitute 0.268 mol, but condition 35 of the fact that dimethyl methylal. The amount of mercaptan is Example 10. For those as in Example 3, hydrogen sulfide was introduced into the reaction mixture at a rate of 38 l / h. 153 mmol of octene-1 dissolved in diglyme at the rate of 1.274 mol / L are irradiated, and solution 40 contains the same photoinitiators as in Example 3. The temperature is maintained at about 0 ° C. After 5 min, 81 mmol of p-octyl mercaptan is formed.
    PRI me R 11. Under the same conditions - ^^ s as in example 3, and the flow rate of hydrogen sulfide 38 l / h irradiated with 67.7 mmol of dodecene-1, dissolved in diglyme at a concentration of 0.564 mol / l at 11 ° C. 3 minutes after the start of irradiation, 48.2 mmol of p-dodecyl mercaptan is formed.
    PRI me R 12. Obtaining mercapto-11-methylundecane.
    A solution of 200 ml of methylundecenate in 660 ml of diglyme containing 1 g of 2 g of benzophenone and 1.8 g of triphenylphosphite - is introduced into the apparatus according to example 4, the injection is carried out continuously
    97Y97 6 under pressure 5 6θΡ, with flow
    200 ml / h The consumption of hydrogen sulfide passed through the reaction mixture is 120 l / h, the process is carried out at 15 ° C. 94 g of mercaptomethylundocanate and 3 g of the corresponding symmetric sulfide are extracted from the effluent stream, the selectivity for mercaptan is approximately 97%.
    Example ^. 350 ml of diethylene glycol dimethyl ether (diglyme) are poured into a 500 ml glass solution. It is saturated with hydrogen sulfide and propylene at a pressure of 3 bar. As a result, 5 mol of hydrogen sulfide per mole of CHjCEkCHa. Diglyme contains per liter 0.006 mol of thiobenzophenone and 0.0022 mol of triphenylphosphite.
    42-watt sodium lamp (yellow light with a wavelength of 588.9 to
    689.5 nm) immersed in a liquid. The latter is stirred and cooled from the outside to 18 + 2 ° C. "
    After 34 minutes, propylthiol is formed. The yield is 82%, the selectivity relative to propylene is 86%.
    PRI me R 14. The procedure is the same as in example 13, but instead of propylene use octene-1. The yield of octyl mercaptan is 84%. The selectivity relative to octene-1 is 89%.
    权利要求:
    Claims (6)
    [1]
    In the case of a light source with a wavelength range of 300-600 nm, a mixture of benzophenone and thiobenzophenone is preferably used. Benzophenone and / or thiobenzophenone are preferably used in an amount of 0.001-0.05 mol / h. Ethylene glycol ether or an aromatic or aliphatic hydrocarbon or methylal is preferably used as a solvent. The main feature of the process is to conduct the process in the presence of benzophenone and / or thio-o-benzophenone in an organic solvent at 0-20 ° C. Examples 1-3. A classical type Pyrex photochemical reactor equipped with a submersible coaxial lamp is used, the base of the vessel being fused to ensure good diffusion of hydrogen sulfide and propylene gases. The irradiated volume is 130 ml. The reactor is thermostatically controlled by a double external bushing head operating continuously when using the appropriate pressure; the gas flow rate is kept constant during the experiment and is 30 l / h for hydrogen sulfide and 28 l / h for propylene. Diethylene glycol dimethyl ether is used as a solution of | The temperature at which the hydrogen sulfide and propylene are saturated is 0 ° C. The concentration of the photosensitizer corresponds to the optimal intensity profile of the radiation absorbed in the reactor. The light source is a low pressure, reverse-emission mercury lamp with a maximum at 350 nm. The power of the light source is 8 watts. After about 35 minutes, the amounts formed are (see tabcaptans to the face). 1Benz Phenone0, OUi 0.12 2Tridekilfosfit0, 66S1 0.07 Continuation of the table From example 3 it is seen that the combined use of benzophenone and phosphite / results in the amount of mercaptan in excess of 2.57 times the amount of mercaptan obtained using only phosphite. Example. Preparation of p-propanethiol The photochemical reaction is carried out in a 250 ml Pyrex cylindrical reactor equipped with a submerged coaxial lamp. Cooling and stirring the reaction mixture is carried out using an external supply, which is cooled in such a way as to maintain the temperature at 18 ° C in the external environment. The reactor is equipped with a fluorescent lamp of power W, with a maximum at 350 nm. 160 ml of diethylene glycol dimethyl ether (diglyme) are introduced into the reactor and the solvent is saturated under a pressure of 3 bar with a gas mixture of hydrogen sulphide and propylene. The consumption of hydrogen sulfide is 90 l / h, the consumption of propylene 30 l / h. These costs are kept constant throughout the entire process. A pulsation smoother, located at the inlet of the gas flow against the flare, allows to maintain a constant pressure in the reactor. The system is connected to a safety valve, which is under backpressure. The electrically driven valve, which controls the level of reagents, allows for continuous removal of effluents formed after the passage of the squeezing device, which is a grid. The solvent contains 0.0055 mol of benzophenone and 0.0022 mol of triphenyl phosphite per liter of solution; it is supplied continuously by means of a metering pump with a flow rate of 350 ml / l. While a steady state is established in the reactor, the volume of the reaction mixture is kept at the level of ml. In such a reactor, 20.13 g of p-propylthiol and k, Q g of dipropyl sulfide are obtained continuously per hour. Consequently, the yield of the measure of captan (by mass) is 83.3%. The mercaptan is recovered by distillation after separation of the residual hydrogen sulfide and propylene, which are recycled to the cycle. EXAMPLE 5 The same operations are performed as in the example enter 120 l / hydrogen sulfide and 10 l / h propylene. The amount of mercaptan obtained per hour is 21.5 g, the yield is 90. EXAMPLE 6 The same operations as in Example 1 are carried out, except that butene-1 is used instead of propylene, to obtain 0,280 mol of butylmercaptan. An example. The same operations were carried out as in Example 1, except that thiobenzophenone (5-1 O mol / l) was used instead of benzophenone (all other conditions remained unchanged). The amount of mercaptan obtained is 0.15 mol. EXAMPLE 8 The same operations are carried out as in Example 1, except that instead of diethylene glycol, solvent is used before decane. The mercaptan output is. Example 9: The same steps were carried out as in Example 1, except that dimethyl ether was replaced with methylal. The amount of mercaptan formed is 0.268 mol. PRI me R 10. Under the same conditions as in Example 3, hydrogen sulfide is introduced into the reaction mixture at a flow rate of 38 l / h. The irradiation is subjected to 153 mmol of octene-1, dissolved in diglyme at the rate of 1 mol / l, and the solution contains the same photoinitiators as in Example 3. The temperature is maintained at about 0 ° C. After 5 minutes, 81 mmol of p-octyl mercaptan is formed. PRI me R 11. Under the same conditions as in example 3, and with a consumption of hydrogen sulfide of 38 l / h, 67.7 mmol of dodecene-1, dissolved in diglyme at a concentration of 0.56 mol / l at 11 ° C, is irradiated . Three minutes after the start of irradiation, 48.2 mmol of p-dodecyl mercaptan are formed. PRI me R 12. Obtaining mercapto-11-methyl undecanate. A solution of 200 ml of methyl undeunate in 660 ml of diglyme containing 2 g of benzophenone and 1.8 g of triphenylphosphite in 1 liter is introduced into the apparatus according to example 4, the injection is carried out continuously under a PR of 5 bar with a flow rate of 200 ml / h. The flow rate of hydrogen sulfide passed through the reaction mixture is 120 l / h, the process is carried out at 15 ° C. 9 g of mercaptomethyl sundokanate and 3 g of the corresponding symmetric sulfide are extracted from the stream of effluents, the selectivity for mercaptan is approximately 97%. Example 13: 350 ml of diethylene glycol dimethyl ether (diglyme) are poured into a 500 ml glass solution. It is saturated with hydrogen sulfide and propylene at a pressure of 3 bar. As a result, mol of CHjCH CH2 is 5 mol of hydrogen sulfide. Diglyme contains per liter 0.006 mol of thiobenzophenone and 0.0022 mol of triphenyl phosphite. A t2-watt sodium lamp (yellow light with a wavelength of 588.9 to 689.5 nm) is immersed in a liquid. The latter is stirred and cooled from the outside to 18 + 2 ° C. After 3 minutes, propylthiol is formed. The yield is 82, the selectivity for propylene is 86. P and measures Tt. The order of operation is the same as in Example 13, but instead of propylene, octene-1 is used. The yield of octyl mercaptan is 84. The selectivity with respect to octene-1 is 89%. Invention T. The method of producing alkyl mercaptans by photochemical reaction of olefin and hydrogen sulfide in the presence of phosphite at a pressure of 1-5 atm, characterized in that, in order to simplify the process, the latter is carried out in the presence of benzophenone and / or thiophenofenone in an organic solvent at a temperature of 0- 20 C.
    [2]
    2. The method according to claim 1, characterized by the fact that benzophenone is used when irradiated with a wavelength of 300-400 nm.
    [3]
    3. The method according to claim 1, is also distinguished by the fact that when irradiated with light with a wavelength of 350-600 nm, thiobenzophenone is used.
    [4]
    4. The method according to claim 1, characterized by the fact that in the case of a light source with a wavelength range of 300,600 nm, a mixture of benzophenone and thiobenzophenone is used. ;
    79710978
    5. Method no. 1, about t l and h and y - or aromatic, or aliphatic u and with the fact that benzophenone and / or hydrocarbon, or methylal. Thiobenofenone used in quantitative sources of information,
    [5]
    be 0,001-0,05 mol / l. taken into account during the examination
    6. The method according to claim 1, of tl and h and h-1b2, published. 1955.
    [6]
    u and with the fact that as a solution-2. US Patent No. З050 + 32, cl. 20 solvent uses ethylene glycol ether 162, published. 19bЗ (prototype).
    J 1. US Patent No., cl.
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    同族专利:
    公开号 | 公开日
    PL215364A1|1980-01-28|
    FR2424907A1|1979-11-30|
    DE2960262D1|1981-05-07|
    NO145914C|1982-06-23|
    BE875988A|1979-11-05|
    EP0005400B1|1981-04-15|
    IT7922292D0|1979-05-02|
    ES480160A1|1980-04-01|
    JPS6256869B2|1987-11-27|
    JPS54145606A|1979-11-14|
    PL120101B1|1982-02-27|
    IT1112504B|1986-01-20|
    EP0005400A1|1979-11-14|
    CA1124202A|1982-05-25|
    NO791463L|1979-11-06|
    BR7902713A|1979-11-27|
    US4233128A|1980-11-11|
    FR2424907B1|1980-09-19|
    NO145914B|1982-03-15|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7813341A|FR2424907B1|1978-05-05|1978-05-05|
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