• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:

    公开号:SU727138A3
    申请号:SU772455510
    申请日:1977-02-25
    公开日:1980-04-05
    发明作者:Декор Жан-Пьер
    申请人:Рон Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of total sulfones (Formula S07KR,, Ch LJL Jf, which, if m -1 and p O, represents a hydrogen atom and R2. Represents a methyl radical; or if a hydrogen atom; R is a hydrogen atom, or when normal or isostructural, kil C,) —Sb is subjected to the interaction of α-halo-acetals of ethylene with the general formula of new aldehydes at high temperatures in the presence of a catalyst. Although the aloidalkoxylation method is also applicable to the synthesis of III-haloaldetal aldehydes, including a double conjugated bond system, obtaining products by this method has a complication due to the inaccessibility of the starting materials, in addition, the yield reaches 75%. The aim of the invention is to simplify the process and increase the yield of the target product. According to the proposed method for producing sulfones of formula (I) by reacting a sulfone of the general formula (I in which m о or 1 and R and R are defined as before, with ethylene aldehyde halogen acetal at a temperature of (-) 100 g (+) 150C in a polar aprotic solvent, in the presence of the main agent, as the acetal halogen of ethylene aldehyde, 0-halogenacetal of the general formula RB .OR L J. X in which H2 g Rg is used, is defined in the same way as before, p O or 1, , with the sum m + n 1; X is hapogen. The proposed method allows to obtain the target product kt with a yield of up to 91% using more available halogen acetals. The reaction is carried out in the aprotic polar nature of the solvent and in the presence of a basic agent that has sufficient activity to anionize the sulfone used. Dimethylformamide is used as a photo polar polar solvent. dimethylacetamide, dimethyl sulfoxide, N-methylpyrr lidone, hexamethylphosphoric triamide. The main agents are miners; l or organic compounds: alkaline lithium alkaline metacal, hydrides or amides, alkaline non ferrous metals, organometallic compounds such as organozinc compounds, organolithium compounds magniyorga nical compound. They can be used individually or together with another basic agent intended to neutralize the hydrohalic acid which forms it. In the case when the main anionizing agent is used 1: apparently, its amounts in the reaction mixture should be sufficient to ensure neutralization of the acid formed. This amount also depends on the methods used and the reactivity of the reaction products with respect to this basic agent. For these various considerations, it may be advantageous to introduce into the reaction a smaller amount of anionizing agent and to add another basic agent in relation to which the reaction products are less sensitive and which is sufficient to neutralize the resulting acid. The reaction can be carried out at a temperature of from (-) 100 to (+) depending on the nature of the products used and the products obtained and preferably in an inert atmosphere, for example in argon. Compounds of general formula (IV) can be prepared by reacting a tertiary aliphatic saturated alcohol hypohalogenite with an aldehyde of general formula AjAvj in which R -} has the above values and p O or 1, in the presence of a primary aliphatic saturated alcohol of the general formula in which R has the above value. Used hypohalogenites of tertiary aliphatic alcohols before-. are preferably chlorine-containing brome bromides. Tertiary aliphatic saturated alcohols are usually used as hypohalogenites because of the convenience and availability of tert.-butanol hypohalogenic derivatives, however, hypohalogenic derivatives of higher alcohols containing up to 13 carbon atoms are also suitable. Typically, a tertiary aliphatic saturated alcohol hypohalogenate is used as a solution in an organic solvent inert under operating conditions, such as a liquid lower aliphatic hydrocarbon, such as pentane, an aromatic hydrocarbon, such as benzene, toluene, xylenes, or an aliphatic or aromatic halogen-containing hydrocarbon. The reaction temperature is not critical and may be, for example, from (-) 40 to (+) 80 ° C. Preferably, they are usually operated at a temperature below 0 ° C, for example, about (-), in order to avoid a noticeable decomposition of the reagent. Usually, the corresponding quantities of tertiary saturated aliphatic alcohol and aldehyde hypohalogenite of general formula (V) are close to stoichiometric, but an excess of one or the other of these reagents can be used without hindrance. Usually, it is enough to use the stoichiometric amount of alcohol of the general formula KdON; however, it is preferable to use an excess of this reagent, which then serves as the reaction medium. In order to increase the reaction rate, it is preferable to use a catalytic amount of a strong mineral acid, known as an acetalization catalyst, such as hydrochloric acid or sulfuric acid. This acid can be introduced into the reaction mixture from the very beginning of the reaction or only after the reaction of the tertiary aliphatic saturated alcohol hypohalite with the aldehyde of the general formula 1.055 g (1.1-10 mol) of tert.-butoxide soda in 4.95 cm of N-methylpyrrolidone is added at -20 ° C in an argo atmosphere and within 5 minutes a solution of 3.44 g of phenyl-B- (2, 6, b-trimethyl-1-yl-cyclohexenyl) -3-methyl-2,4-pentadienylsyl-sulfone 94% purity (1; 1 10 mol) in 5.74 m N-methyl pyrrolidone. After stirring for 5 min with solution 2, ZR8 g (1.135 mol of 2-bromo-1,1-dimethoxy-3-methyl-butene -3 in 4.5 cm N- Methylpyrrolidone. The reaction mixture was then stirred at 0 ° C for 2, 1/4 h, then a follower of 12 cm of diisopropyl ether purified from peroxides and 25 cm of water was added to it for 10 minutes, the aqueous phase was extruded twice in total 20 see diy g opylevogo ether. The organic phases are combined. A solution of 1,1-dimethoxy-3,7-dimethyl- (2,6,6-trimethyl-1-cyclohexen-yl) -2,6, 8-nonatrien-yl-5-phenylsulfone is obtained in this way . , f -t - n (СНз) 2 (1) singlet at 0.97 tlHj (5) singlet at 1.26 (9) singlet at 1.65 СНд (13) singlet at 1.65 N (7) singlet at 5 , 94 N (8) singlet at 5.94 N (11) singlet at 4.05 OCH-9 singlet at 3.11 and 3.2 Output relative to the starting phenyl (trimethyl-2,6,6-cyclohexen-1-yl) - 5-methyl-3-pentadiene-2,4-yl-sulfone is 91%. This product can be converted to the corresponding aldehyde. The resulting solution is stirred at a temperature of about 20 ° C for 1 3/4 h with 0.247 cm of an aqueous 4N solution of sulfuric acid, then is washed successively with 5 cm of an aqueous solution. a saturated solution of sodium bicarbonate and twice a total of 5 cm of water, and dried over anhydrous sodium sulfate. After filtration and cooling to 0 ° C, 0.6275 g of 3,7-dimethyl-9- (2,6,6-trimethyl-l-cyclohexene-yl) -1-oxo-2, 6.8 is filtered off for 15 minutes. -nonatriene Il-5-phenylsulfone, identified by NMR spectroscopy. By concentrating the mother product of the previous product, a residue is obtained, weighing 3.970 g, in which 8, 1 22 10 mol of 9- (3,7-dimethyl-2,6, 6-trimethyl-1-cyclohexen-yl) -1 are found by NMR. -oxo-2,6,8-nonatrien-yl-5-phenylsulfone and O, 5310 mol of the starting phenyl-5- (2,6,6-trimethyl-1-cyclohexen-yl) -3-methyl-2, 4- pentadiene-sulphone. The yield of aldehyde sulfone is 91% with respect to the initial converted sulfone. The starting 2-bromo-1,1-dimethoxy-3-methyl butene-3 can be prepared as follows. To a solution of 5.04 g (b-Yu mol) 3-methyl-butene-2-al (or prenal) in 50 cm of methanol, cooled to about -20 ° C, was added 1.6 cm of concentrated sulfuric acid, then for 90 minutes - 77.5 cm of a pentane 0.774 M solution of tert.-butylgipobromide, then the temperature is allowed to rise to within 30 minutes. The reaction mixture is then poured into 100 containing 11.16 g (0.9-10 mol) of sodium bicarbonate. The aqueous phase is separated, extracted three times with a total of 75 cm of pentane. The organic phases are combined, washed with 30 cm of water, then with 30 cm of a saturated aqueous sodium bicarbonate solution and dried over anhydrous sodium carbonate. After concentration to dryness under reduced pressure of about 20 mm Hg, at a temperature below 50 ° C, a residue of 12.92 g is obtained consisting of a mixture of 2-bromo-1, 1-dimethoxy-3-methyl-butene-3 and 2 β-bromo-1,1,3-trimethoxy-3-methyl butene identified by NMR. By distillation, 6.55 g of 2-bromo-1,1-dimethoxy-3-methyl butene-3 was isolated (bp 48.5 ° C at 0.2 mm Hg).
    权利要求:
    Claims (1)
    [1]
    1. Patent of the USSR 473360, cl. C 07 C 147/04, declared 1973 (prototype).
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    同族专利:
    公开号 | 公开日
    US4110538A|1978-08-29|
    CA1072571A|1980-02-26|
    FR2342282B1|1979-07-20|
    JPS5725033B2|1982-05-27|
    DE2708210C2|1984-09-06|
    NL175817B|1984-08-01|
    NL175817C|1985-01-02|
    SE422457B|1982-03-08|
    BE851782A|1977-08-24|
    NL7701706A|1977-08-29|
    JPS52102246A|1977-08-27|
    GB1521015A|1978-08-09|
    CH618423A5|1980-07-31|
    SE7702071L|1977-08-26|
    IT1085866B|1985-05-28|
    DD129109A5|1977-12-28|
    DE2708210A1|1977-09-01|
    FR2342282A1|1977-09-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3781313A|1971-01-20|1973-12-25|Rhone Poulenc Sa|Sulfone intermediates for the synthesis of vitamin a|
    FR2138212B1|1971-05-19|1973-05-11|Rhone Poulenc Sa|
    BE794873A|1972-02-02|1973-08-01|Rhone Poulenc Sa|NEW DIMETHYL-1,6 HEXADIEN-1,5 YLENE RANGE SULPHONES|
    BE794872A|1972-02-02|1973-08-01|Rhone Poulenc Sa|NEW SULPHONES DERIVED FROM DIMETHYL-1,5 HEXADIENE-1,5 YLENE|
    BE794944A|1972-02-04|1973-08-02|Rhone Poulenc Sa|NEW UNSATURATED SULPHONES CONTAINING A CARBONYL FUNCTION|
    BE794943A|1972-02-04|1973-08-02|Rhone Poulenc Sa|NEW METHYLENIC SULPHONES IN THE TERPENES SERIES|
    US3906967A|1974-05-08|1975-09-23|Maytag Co|Dishwasher|BE794872A|1972-02-02|1973-08-01|Rhone Poulenc Sa|NEW SULPHONES DERIVED FROM DIMETHYL-1,5 HEXADIENE-1,5 YLENE|
    US4883887A|1987-07-09|1989-11-28|Hoffmann-La Roche Inc.|Sulfone polyene intermediates|
    US5185468A|1990-06-14|1993-02-09|Kuraray Company Ltd.|Process for producing β-carotene, and intermediate compounds useful for the process|
    DE4123994A1|1991-07-19|1993-01-21|Basf Ag|IMPROVED METHOD FOR PRODUCING POLYENES|
    CN103183591B|2007-01-31|2016-01-20|Dic株式会社|4 '-dialkoxymethyl bis cyclohexane-4-base methyl alcohol and manufacture method thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7605244A|FR2342282B1|1976-02-25|1976-02-25|
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