• 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:
    The method of producing 2,3-dihydro-2, 2-damethyl-7-oxibenzo-furan is heated by heating o-metalloxyphenol, in order to achieve the yield of the target product, the process is carried out in the presence of the catalyst is an aluminum or aluminate powder of the formula .OR OR where R is lower alkyl, taken in an amount of at least 0.008 mol of catalyst per mole o-4 metalloxyphenol, and heating O) is carried out at 120-150 ° C.
    公开号:SU1153828A3
    申请号:SU803213102
    申请日:1980-12-05
    公开日:1985-04-30
    发明作者:Мишле Даниель；Верасини Серж
    申请人:Рон-Пуленк Агрошими (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the preparation of 2,3-di-hydro-2, 2-dimethyl-7-hydroxybenzofuran (DDB), which is used in the synthesis of 2,3-dihydro-2,2-dimethyl-7-benzofuranylmethyl carbamate, a polyvalent insecticide - carbofuran. A known method for producing 2,3-dihydro-2, 2-dimethyl-7-hydroxybenzofuran by heating ortho-methyl pyrocatechin at 190-2 l. The disadvantage of this method is the low yield of the target product (v48.2%). There is also known a method for producing 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran by heating ortho-metalloxy phenol at 200-275 ° C 2. The disadvantage of this method is also the low yield of the target product (37%). The closest to the technical essence and the achieved effect is the method of obtaining 2 3-dihydro2, 2-dimethyl-7-hydroxybenzofuran by heating the ortho-metalloxyphenol in an autoclave at 170-250 ° C in the presence of water or water and an inert organic solvent or inert organic solvent followed by addition of water h. However, this method is not sufficiently high yield of the target product (69-75%). The purpose of the invention is to increase the yield of the target product. The goal is achieved by the method that o-metalloxyphenol is heated at 120-150 ° in the presence of aluminum or aluminate powder of the formula t Alf OR o, where R is lower alkyl, in an amount of at least 0.008 mol of catalyst as catalyst per mole of thallyloxyphenol and heating is carried out at 120-150 ° C. It is known to use aluminum phenol when heating a tert-butylphene ether, whereby the ether is split with the release of isobutene and fixing the isobuteum on phenol to produce o-tert-butylphenol. 82 In the proposed method, aluminates of the indicated formula I use lower aluminum alkoxides, preferably aluminum isopropylate. The process time depends on the temperature, i.e. the higher the temperature, the shorter the duration of the process (usually 15 minutes - 20 hours). The catalyst is preferably used in the amount of 0.0080, 3 mol / mol of the starting metalol oxyphenol. At the end of the reaction, the resulting DSOB is obtained by any known method, for example, by distillation. However, sometimes it is not necessary to provide DCDB and then it is sufficient to leave it in the reaction medium. The aluminum derivative can be removed by washing the reaction mass with an aqueous solution of a strong acid. For convenience, hereinafter, the abbreviation TT (ME) means the degree of conversion of ortho-metalloxyphenol, R T (DFS), the yield of DDB relative to the converted ortho-metalloxyphenol. Example 1. The apparatus used is a 20 ml flask equipped with a reflux condenser and magnetised with a rod. 0.0207 g of isoprochol aluminum (IjOlO mol), 1.7012 g of o-methyllyloxyphenol (1.037 -) are sequentially loaded into it. The mixture is heated for 12 hours while being transported, then cooled to room temperature. Add 20 ml of aqueous 2N. hydrochloric acid solution, 20 ml of ethyl acetate and all vigorously stirred in a separatory funnel. After separation of the two phases, the organic phase is washed with 20 ml of distilled water, which is combined with the aqueous phase; under stirring (spinning), the aqueous phase is washed with 20 ml of ethyl acetate, which is combined with the first organic phase. The combination of organic phases gives 1,208 g of DDB and contains, in addition, 0.195 g of unconverted ortho-meta-phenoxy-phenol: TT (IU) 88.5%. RT (DDB) 80.2%. Comparative experience. According to the conditions and temperatures of Example 1, from 1.043 g of ortho-metalloxyphenol without the use of the alcuminic derivative: a mixture is obtained, containing
    U, 189 g of unconverted ortho-metalloxyphenol, 0.0126 g DDAB, 0.520 g of ortho-metallic pyrocatechin, 0.188 g of metallic vapor pyrocatechin, or TT (No.;) 81.9%, RT (DDB) 1.5%. From this experience, it follows that, in the absence of a catalyst, the cyclization of ortho-metal pyrocatechin in the DCDB is carried out only to a very small extent and that the TT (IU) is lower than that obtained with the catalyst.
    Example 2. Follow the procedure of example 1 using the same apparatus, and starting from 0.0436 g of aluminum iso-opyl acetate (2.1–10 mol), 1.7164 g of o-metalloxyphenol (1.04610 mol)
    The mixture is heated at 140 ° C. for 6 hours with stirring. Thus, 1.080 g of DDB is obtained and 0.343 g of unconverted o-metalloxyphenol or TT (IU) 80.0% of RT (DDB) of 78.6% remain.
    . PRI me R 3. Follow the procedure of example 1 using the same apparatus and starting from 0.0257 g of aluminum isopropylate (1.2 10 mol), 2.2789 g of o-metalloxyphenol (1.4).
    The mixture is heated at 150 ° C for 1 h with stirring TT (IU) 75.1%, CT (DCIB) 75.4%.
    - Example 4. The procedure of example 1 is followed using the same equipment and starting with 0.239 g of aluminum isopropylate (11,); 1.7548 g of o-metalloxyphenol (1.07.1)
    The mixture is heated at 150 ° C for 15 minutes with stirring, TT (IU) 96.4%, RT (DCOB) 71.7%.
    Example 5. In the procedure described in example i, the apparatus was sequentially charged with 0.266 g of aluminum isopropyl (13.0-U), 2.156 g of o-metalloxyphenol (1.31 × 10 mol), 5 ml of p-xylene.
    The mixture is heated at 140 ° C for 2.5 hours with stirring, then cooled to room temperature. Aqueous 2n is added. a solution of hydrochloric acid, 50 ml of methylene chloride and everything is stirred in a separating funnel. After being filtered on a Buchner funnel to remove insoluble particles and separating the two liquid phases, the aqueous phase is washed with 2 times 25 ml of methylene chloride, which is then combined with the organic phase.
    The combination of organic phases gives 1,666 g of DDB and contains 0,072 g of unconverted o-metalloxyphenol, or TT (IU) 96, (DCOB) 79.9%.
    Example 6. The procedure of Example 5 is followed using the same apparatus and starting from 0.244 g of aluminum isopropylate (12–10 mol), 2.1658 g of o-metalloxyphenol (1.32–10 mol) of 5 ml of p-xyllol.
    The mixture is heated at 120 ° C for 3.5 hours with stirring. Thus, 1.456 g of DDB is obtained and 0.298 g of unconverted o-metalloxyphenol remains, or TT (IU) 86.2% of IT (DDB) is 78.0%.
    Example 7. The procedure of Example 5 is followed using the same apparatus, starting from 0.052 g of aluminum isopropylate (1.2 mol) (t, e.O., 008M per 1 m o-metalloxyphenol), 2.4384 o-metalloxyphenol (1.5 vlO mol), 6 ml of xylene.
    The mixture is heated at 140 ° C for 16.5 hours with stirring. The TT (IU) is 98.5%, and the AT (DCIB) is 74.0%.
    Example 8. Follow the procedure of example 5 using the same apparatus and starting from 0.132 g of aluminum isopropyl (6.4 -10 mol), 2.002 g of o-metalloxyphenol (1.2-10 mol), 5 ml of anisole.
    The mixture is heated at 130 ° C for 6 hours with stirring. TT (IU) 86.9%, RT (DDB) 74.8%.
    Example 9. Follow the procedure of example 5 using the same hardware and starting from 0.822 g of aluminum isopropylate (40); 2,119 g of o-metalloxyphenol (1.3 10 mol), 5 ml of n-decane.
    The mixture is heated at 100 ° C for 1 h with stirring. A mixture is obtained containing 1.286 g of DDB, 0.177 g of o-metallopirocatechin (O, 1110 mol), but not containing more than o-methyllyloxyphenol, TT (ME) 100.0%, RT (DOB) 60.7%.
    Example 10 A 25 cm autoclave with a capacity of 25 cm was successively charged with 0.237 g of alcmini isopropylate (11.6-10 mol of 2.0473 g of o-metalloxyphenol (1.2410 mol); 6 ml of isopropyl alcohol.
    The autoclave is heated at 3 hours in a bath with a Wood alloy, then cooled to room temperature. The reaction mixture is partially concentrated, then treated with 50 ml of aqueous 2n. hydrochloric acid solution and 50 ml of methylene chloride. Subsequent processing is ideal for example 5. Thus, 1.564 g of DDB is obtained and 0.036 of the unconverted o-metalloxyphenol or TT (IU) is left at 98.2%, and (DDB) is 77.8%. PRI and m er 11. Follow the procedures of example 10, work in an autoclave, which is loaded with 0.263 g of isoprop aluminum lat (12.9 1 S mol), 2,0087 g of o-metalloxyphenol (1.2210 mol), 6 ml n dean. The mixture is heated for about 3 hours, then treated by example 10, TT (IU) 98.6Z, and (DDB) 73.5%. Example 12, Into the apparatus of Example 1, 0.039 g of aluminum poropsy (14.3.), Sequentially dehydrated by treatment with aqueous saline, 2.186 g of o-methyloxyphenol (1.33–10 mol), 10 ml xylene. The mixture is heated to 140 ° C, about 1 mg of mercury chloride is added and gases are immediately released. The reaction mixture is held at 140 ° C for 1.5 hours while stirring, then it is cooled to room temperature. The treatment was identical to Example 5. Thus, 1.093 g of DDB was obtained and 0.768 g of unconverted o-metalloxyphenol or TT (no.) 64.9% remained, and CT (DDB) 77.1%. Example 13. In the apparatus described in example 1, 0.0305 g (1) (), of phenol, 1.6017 g of o-metal-shoxophenol (9.77.10 mol), prepared by exposing aluminum isopropioniara to phenol, is loaded. The mixture is heated for 15 hours at 130 ° C. The solution is treated as in example 1, 0.338 g of unconverted o-metalloxyphenol, 0.975 g DCDV or TT (IU) 78.9%, CT (DCDB) 75.6% are obtained in the same way. This method allows to increase the yield of the target product up to 80%.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING 2,3-DIGIDPO-2,2-DIMETHYL-7-OXYBENZOFURANE by heating ο-metalloxyphenol, which is based on the fact that, in order to increase the yield of the target product, the process is carried out in the presence of aluminum powder as a catalyst or aluminate of the formula ^ 0R Αίς-ΟΗ x 0R where R is lower alkyl, taken in an amount of not 0.008 mol of o-metalloxyphenol catalyst, and is carried out at 120-150 ° G.
    less per mole of heating f
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    同族专利:
    公开号 | 公开日
    FR2470768B1|1983-02-04|
    YU303680A|1983-01-21|
    EP0030511B1|1984-02-29|
    IE802512L|1981-06-07|
    BG35188A3|1984-02-15|
    FR2470768A1|1981-06-12|
    IL61424D0|1980-12-31|
    JPS6135191B2|1986-08-12|
    YU41369B|1987-02-28|
    AT6424T|1984-03-15|
    PT72175A|1981-01-01|
    PL136260B1|1986-02-28|
    ES497479A0|1982-09-16|
    IL61424A|1985-04-30|
    EP0030511A1|1981-06-17|
    DK154140B|1988-10-17|
    ES8304109A1|1982-09-16|
    KR840001020B1|1984-07-20|
    CA1157875A|1983-11-29|
    HU185804B|1985-04-28|
    DK154140C|1989-03-06|
    JPS5697279A|1981-08-05|
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    RO80924B|1983-02-28|
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    PT72175B|1982-07-05|
    DK520480A|1981-06-08|
    DE3066770D1|1984-04-05|
    RO80924A|1983-02-15|
    US4324731A|1982-04-13|
    IE51695B1|1987-02-18|
    BR8007966A|1981-06-23|
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    US3927118A|1973-12-21|1975-12-16|Crown Zellerbach Corp|Process for monoetherification of polyhydric benzenes|JPH0215548B2|1981-07-29|1990-04-12|Ootsuka Kagaku Kk|
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    法律状态:
    优先权:
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    FR7930645A|FR2470768B1|1979-12-07|1979-12-07|
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