• 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:
    <P> Preparation of a thiophene by the action of H2 S on an organic substance containing oxygen or sulfur. The substance used is an unsaturated carbonyl or thiocarbonyl compound, in particular an aldehyde, thioaldehyde, ketone or thioketone. The reaction is preferably carried out at 250 to 500 ° C. on an alumina catalyst containing an alkaline or alkaline earth oxide. </ P> <P> The process makes it possible to obtain unsubstituted or substituted thiophene with high yields and selectivities, exceeding 70%. </ P>
    公开号:SU793396A3
    申请号:SU772556953
    申请日:1977-12-21
    公开日:1980-12-30
    发明作者:Барро Жоэль；Гисне Мишель；Люсьян Жак；Морель Раймон
    申请人:Сосьете Насьональ Елф Акитэн (Продюксьон) (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING TIOPHENES
    one
    This invention relates to an improved process for the preparation of thiophenes of the general formula I
    where R, R, Rj and P3 are independently of each other hydrogen or lower alkyl,
    or R and R-2. or R-together the group -CH CH-CH CH-, which are used in various organic syntheses.
    A known method for the preparation of thiophenes of the general formula I is that the compound of the general formula
    RCH, C dCOKj
    I) R, RZ
    where R, R, Rj and Ri are as defined above, they are reacted with carbon disulfide in the presence of alumina at 2006 ° C. The outputs of the target products do not exceed 50% lj.
    The disadvantage of this method is the use of toxic and explosive carbon disulfide.
    The purpose of the present invention is to simplify the process in order to eliminate this drawback.
    The goal is achieved by the described method of producing thiophenes of the general formula 1, namely, that a compound of the general formula H is reacted with hydrogen sulfide in the presence of an alkyline oxide with
    10 200-500 ° C. Process preferably
    carried out at a molar ratio of the compound of general formula 1 and hydrogen sulfide 1: 2-5. Preferably, an oxide containing catalyst is used.
    5 or an alkali metal or alkaline earth metal sulfide.
    A distinctive feature of the method is the use of hydrogen sulfide as a sulfur-containing compound.
    Example 1. Various catalysts are used at 400 ° C and at a molar ratio of hydrogen sulfide - crotonaldehyde 5, contact time
    25 1 s. Pre-heated reactor continuously enters liquid; aldehyde simultaneously with hydrogen sulfide. After passing through the reactor, the substances are condensed, collected and
    30 is subjected to separation. In tab. Table 1 shows the results for various catalysts (activity after 30 hours of action (jf production of thiophene, mol / h / kg of catalyst) and specific surface of the catalyst, m / g).
    The optimum content of potassium oxide is between 3.2 and about 1-3%. At 15.3% potassium oxide, the activity begins to decrease with respect to pure alumina A, although the selectivity for thiophene is higher. The maximum activity, in combination with a high selectivity of 76%), is between 7 and 10%.
    For these catalysts, the activity was determined at different operation times (Table 2.)
    EXAMPLE 2. The experiments were carried out under the conditions of Example 1.
    The catalysts are prepared by impregnating alumina with solutions of potassium and sodium hydroxides, respectively. or magnesium and calcium acetate, respectively. The amounts of potassium, sodium, magnesium and calcium oxides introduced into alumina are equimolar.
    The activity and selectivity of catalysts after 30 hours of consumption are shown in Table. 3
    These results show that potassium and sodium oxides have the same effect; on the contrary, calcium and magnesium oxides lead to rapid deactivation of the catalyst and activity after 30 hours of consumption is close to the original alumina.
    Froze Experiments were carried out to obtain thiophene at 400 ° C with a ratio of hydrogen sulfide-crotonic aldehyde 5 and a contact time of 0.75 s with alumina with the addition of 7% and with alumina A with the addition of 7.7%. The results obtained after different operating times of the catalysts are given in table. four.
    After setting the mode to about 20 hours, the deactivation is relatively slow and regular in time, it is about 0.12% / h, the selectivity of thiophene is 85% all the time.
    By-products of light hydrocarbons Cj, mainly obspecific surface of the catalyst, m / g
    335 4.3 77.0 12.0 2.5
    O 3.2 265 8.4 74.5 7.0 1.5
    once propene and butadiene are easily removed from the reaction mixture.
    Example 4: Effect of Crotonaldehyde Partial Pressure and Hydrogen Sulfide.
    The catalyst consists of alumina A from 7.7%. The reaction is carried out at 400 ° C with a contact time of 0.5 s.
    In tab. 5 shows the results of experiments with changes in the pressure of crotonaldehyde and hydrogen sulfide.
    From these results it can be seen that an excess of hydrogen sulfide contributes to the high selectivity of the process.
    Example 5: Effect of temperature and contact time on process selectivity in an industrial reactor.
    In an industrial reactor, experiments were carried out to obtain thiophene, with a molar ratio of hydrogen sulfide-crotonic aldehyde 5, on an alumina catalyst with an addition of 7.7%. They work with high conversion of crotonaldehyde at different contact times and temperatures. In tab. b shows the results of these experiments.
    PRI me R b. From various carbonyl compounds, thiophene and substituted thiophenes are obtained.
    The reaction is carried out at 400 ° C on alumina A containing 7.7%. The ratio of the partial pressures of hydrogen sulfide and the original carbonyl compound 5.
    The results are presented in the following table. 7, the contact time of the reaction medium and the catalyst is given in equivalent m / F, where the catalyst mass is in grams and the F-gas flow, mol / h.
    Example 7. Under the conditions of Example B, benzo (c) thiophene is synthesized, starting from o-toluene dehydrate.
    The ratio km / F is 9.1, the conversion of aldehyde is 28% and the selectivity of benzo (c) thiophene is 14%.
    PRI me R 8. Get benzo (b) thiophene by the method of example 7, starting from phenyl acetaldehyde CjjHj-TENDER. The ratio m / F is equal to 9.1, the selectivity of 7% with the conversion of phenylacetaldehyde 40%.
    Table
    8.5 17.0
    20 40 60
    Continued table. one
    Table
    Table4
    Continued table. four
    Table 5
    T blitz b
    CHjdH CH-c-CHj
    Penten-3-on-2
    dHj
    CHjCH C - CHO
    2-Methylbuten-2-al
    SI, oh
    I ii
    CHj-d CH-c
    CHj
    4-Methylpenten-Z-one-2
    sn
    l
    CHjdH CH c - bno
    2-Methylpenten-2-al
    CH CHCHO
    Hexene-2-al
    dHjCH2CH2CH about -CHO
    SnI
    CHj
    2-Ethylhexene-2-al
    权利要求:
    Claims (3)
    [1]
    1. A method for producing thiophenes of the general formula 7
    R (
    IT
    where R, R, K, and Rj are independently hydrogen or lower alkyl,
    or R and R-j together, or Rj. together the group —CH — CH — CH — CH—,
    Table 7
    7.5
    50
    2-methylthiophene
    72
    52
    7.5
    77
    3-Methyl ± iofen
    20
    5.0
    70
    2,4-Dimethylthio67
    9.0 54 hair dryer
    8.5 55
    54
    2-ethylthiophene
    60
    9.8 50
    2,4-Diethylthiophene
    50
    the interaction of the compounds of formula F
    ESNGS CCORj
    55
    ) l. | Jc "
    where R, R, Rj and RJ are as defined above,
    with a sulfur-containing compound in the presence of alumina as a catalyst at 200-500 ° C, which is different from the fact that, in order to simplify the process, hydrogen sulfide is used as a sulfur-containing compound. -. H ...-
    [2]
    2. Method no. Item 1, O tl and h a yush and and G in that the catalyst contains an oxide or sulfide of an alkali or alkaline earth metal.
    [3]
    3. The method according to claim 1, wherein the compounds of the general formula and hydrogen sulfide are used in a molar ratio of 1: 2-5, respectively. , Sources of information taken into account in the examination 1. Patent of England No. 1345203, cl. C 23 C, published, 1974 (prototype).
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    同族专利:
    公开号 | 公开日
    US4143052A|1979-03-06|
    JPS5379855A|1978-07-14|
    IT1089132B|1985-06-18|
    FR2375227B1|1979-04-13|
    DE2757816A1|1978-07-06|
    LU78735A1|1978-07-11|
    GB1585647A|1981-03-11|
    NL7714177A|1978-06-27|
    BE861486A|1978-06-05|
    FR2375227A1|1978-07-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2558507A|1945-09-05|1951-06-26|Shell Dev|Production of thiophene compounds from mono-olefins and hydrogen sulfide with alumina catalyst|
    GB1434724A|1972-04-17|1976-05-05|Rech Et Dapplications Scient S|Spasmolytic medicines comprising a vidiquil derivative|
    US3939179A|1973-08-29|1976-02-17|Pennwalt Corporation|Continuous production of thiophene from butane|US4414102A|1981-05-15|1983-11-08|Mobil Oil Corporation|Process for reducing nitrogen and/or oxygen heteroatom content of a mineral oil|
    DE3433813A1|1984-09-13|1986-03-20|Hoechst Ag, 6230 Frankfurt|METHOD FOR ISOMERIZING ALKYLTHIOPHENES|
    DE3643983C2|1986-12-22|1989-05-11|Haar-Czogalla, Rita Von Der, 8152 Feldkirchen-Westerham, De|
    FR2666336B1|1990-08-29|1994-09-02|Elf Aquitaine|PROCESS FOR THE MANUFACTURE OF THIOPHENE.|
    US6225261B1|1992-02-24|2001-05-01|Halliburton Energy Services, Inc.|Composition and method for controlling precipitation when acidizing wells|
    US5622919A|1992-02-24|1997-04-22|Halliburton Company|Composition and method for controlling precipitation when acidizing wells|
    JP3259206B2|1993-09-27|2002-02-25|イハラケミカル工業株式会社|Method for producing 2-substituted benzo [b] thiophene|
    US5514289A|1995-04-13|1996-05-07|Mobil Oil Corporation|Dihydrobenzothiophenes as antioxidant and antiwear additives|
    US5723629A|1995-06-28|1998-03-03|Shell Research Limited|Thiophene synthesis|
    JP2001524114A|1997-04-30|2001-11-27|イーライ・リリー・アンド・カンパニー|Intermediates and methods in the production of benzo [b] thiophenes|
    US6534448B1|2000-11-02|2003-03-18|Halliburton Energy Services, Inc.|Composition and method for acidizing wells and equipment without damaging precipitation|
    US6415865B1|2001-03-08|2002-07-09|Halliburton Energy Serv Inc|Electron transfer agents in well acidizing compositions and methods|
    US6653260B2|2001-12-07|2003-11-25|Halliburton Energy Services, Inc.|Electron transfer system for well acidizing compositions and methods|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7638842A|FR2375227B1|1976-12-23|1976-12-23|
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