• 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:
    A process for the preparation of an optionally substituted 3-phenoxybenzaliehyde, or an acetal thereof, which comprises reacting an optionally substituted 3-bromobenzaldehyde, or an acetal thereoff with a phenol, or an alkali metal salt thereof, in the presence of an aprotic organic solvent and copper and/or a copper compound.
    公开号:SU910113A3
    申请号:SU762439451
    申请日:1976-05-31
    公开日:1982-02-28
    发明作者:Артур Шелдон Роджер；Вильгельмус Ван Дер Меер Иоганнес；Иоган Мульдер Альбертус
    申请人:Шелл Интернэшнл Рисерч Маатсхаппий Б.В.(Фирма)；
    IPC主号:
    专利说明:

      3 9 Pyridine is usually used as an aprotic solvent. The alkali metal salt of phenol is a sodium or potassium salt; however, the sodium salt is most preferable because it provides a higher village (resistance to 3 phenoxybenzaldehyde. Preferably, this salt anhydrous, due to the fact that the presence of water reduces the yield of the target product. Such anhydrous salt can be obtained as a result of the reaction between the phenolic and alkali metal hydroxide, followed by removal of the Water as an azeotropic mixture with toluene or xylene. An alternative to the reaction described above is the interaction between the phenol and the alkali metal alcohol, followed by removal of the alcohol formed by the distillation of the alcohol by the distillation method used in accordance with the proposed method. may be an aromatic hydrocarbon, such as toluene or xylenes (m, e, para-xylene, metaxylene, orthox-lol, an aromatic heterocyclic nitrogen compound such as pi Ridin, 2, /, 6-trimethylpyridine, quinoline or pyridine-M-oxide, dialkylamide, such as dimethylformamide or dimethyl acetamide, sulfoxide, such as dimethyl sulfoxide or tetrahydrothiophene-1, 1-dioxide. Mixtures of these solvents can also be used in accordance with the proposed method. Tribrombenzaldehyde. And phenol or its salt can be used in a molar ratio. However, it is preferable that the molar ratio between benzaldehyde and phenol (or it will be merged in the range from 0.5: 1 to 2: 1 or more, and also that this ratio varies in the range from 0.9: 1 to 1: 1. The reaction time is 1-5 hours. 3-Phenoxybenzaldehyde is reacted with hydrogen cyanide to obtain alpha-cyano-3 phenoxybenzyl alcohol, or 3-phenoxybenzyl alcohol is obtained as a result of hydrogenation. further obtaining of complex 4 esters, cat These are pyrethrin type insecticides Example 1. Concentrated potassium phenol (0.02 mol) is obtained from phenol (0.02 mol) and potassium hydroxide (0.02), followed by removal of the resulting water as an azeotropic mixture with toluene. t, 3-bromobenzaldehyde (0.02 mol), monovalent copper chloride (0.0005 mol) and pyridine - (5 ml) are reacted with refluxing for 2 hours. Next, the mixture is brought to 50 ml by addition of diethyl ether, and the ether solution thus obtained is washed with water (three times 50 ml each time) and dried with Strongly anhydrous sodium sulfate. An analysis by gas-liquid chromatography shows that the conversion of the starting 3 bromobenzaldehyde is 97 with a selectivity to 3-phenoxybenzaldehyde equal to 85. Evaporation of the ether solution and distillation of the residue yields a pure 3 phenoxybenzaldehyde, the boiling point of which is 125 C at a pressure of 0.8 mm mercury. is 7. The indicated 3 Phenoxybenzaldehyde can be purified using the bisulfide complex. Example 2 (comparative. The procedure described in example 1 is repeated using 3 chlorobenzaldehyde. The result is a complex product mixture containing only about 10 3 phenoxybenzaldehyde. Example 3: repeated using acetal 3 bromobenzaldehyde ethylene glycol, the reaction was carried out for 5 hours. As a result of analysis by gas chromatography, the starting material was converted to 90 with a selectivity of 92 to acetyl 3 of phenoxybenzaldehyde ethylene glycol. Example. (compare The procedure described in Example 3 was repeated using acetal 3 hl 6 rbenzaldehyde ethylene glycol. After performing the reaction for 6 hours, the conversion was less than 5. Examples 5-7. The procedure described in example 1 was repeated using pyridine of the three other types of solvents. 5 The table presents the types of voriteley, degree of conversion and 910PZ6 rast on the selectivity relative to 3 data phenoxybenzaldehyde.
    reflux time is 3.5 hours) EXAMPLE 8.O, 05 mol sodium hydroxide and 0.5 mol phenol are stirred in 75 ml of a mixture consisting of industrially derived ortho-xylene, meta-xylene and steam xylene. The resulting water is removed by an azeotropic distillation process using a Dean-Stark apparatus. The suspension of sodium phenol obtained in this way is mixed with 25 ml of pyridine, with 0.05 mol of freshly distilled benzaldehyde and with 0.0025 mol 7 (monovalent copper loride. This mixture is heated at refluxing for 30 minutes. Then the gas-liquid analysis performed chromatography shows that the conversion of 3 bromobenzaldehyde is 97, and the selectivity to 3-phenoxybenzaldehyde is 97. PRI me 9 The procedure described in example 1 is repeated using 3-bromobenzaldehyde and C-non-, toxphenol ta The resulting product is a 3- (-methoxyphenoxy) benzaldehyde with a melting point of 150 ° C at a pressure of 0.1 mm Hg, the yield is 0.10%.
    86
    权利要求:
    Claims (2)
    [1]
    82 Claim 1. Method for preparing phenoxybenzaldehyde derivatives 3 of the general formula T inter II 1 1 H where R denotes hydrogen or methoxy group, characterized in that, in order to simplify the process, alkali metal phenol of the general formula II where R has the above value and Not means an alkali metal, is reacted with 3-bromobenzaldehyde at the boiling point of the reaction mixture in the range from 100 to 200 ° C in an aprotic solvent medium in the presence of copper chloride.
    [2]
    2. The way popl.otlichayus and with the fact that as an apron solvent using pyridine. Sources of information taken into account in the examination 1. Lock G., Kempter F. IJber Derlvatr des Phenglathers. - Monatshefte fur Chemie. 1935, 67, 598-609 (ntototip).
    类似技术:
    公开号 | 公开日 | 专利标题
    Wang et al.2001|The Knoevenagel condensation of aromatic aldehydes with malononitrile or ethyl cyanoacetate in the presence of CTMAB in water
    KR950006791B1|1995-06-22|Process for the preparation of|-para-cyclophane and derivatives thereof
    US4152352A|1979-05-01|Process for the carbonylation of aralkylhalides
    SU910113A3|1982-02-28|Process for producing 3-phenoxybenzaldehyde derivatives
    US4217282A|1980-08-12|Process for making N-|-maleimide
    US4673761A|1987-06-16|Process for preparing anti-inflammatory cycloalkylidenemethylphenylacetic acid derivatives
    US4188341A|1980-02-12|Process for the production of | 2,6-dimethylanilines
    US10364203B2|2019-07-30|Method for preparing phenolics using a catalyst
    US4183861A|1980-01-15|Process for preparing aromatic methylene-dioxy compounds
    JP3663229B2|2005-06-22|Process for producing 4-halo-2'-nitrobutyrophenone compound
    Margaretha et al.1983|Synthesis of imines of. alpha.,. beta.-acetylenic ketones
    US4058563A|1977-11-15|Novel schiff bases
    KOBAYASHI et al.1977|Studies on organic fluorine compounds. XXII. Synthesis and reactions of | benzofurans
    US4162269A|1979-07-24|Purification process for 3-phenoxybenzaldehyde
    Youn et al.2001|Highly diastereoselective additions of methoxyallene and acetylenes to chiral α-keto amidesElectronic supplementary information | available: synthesis and spectroscopic data for 4b, 5g, 6b and 7b. See http://www. rsc. org/suppdata/cc/b1/b100355k
    JPH0615514B2|1994-03-02|Method for N, ω trifluoroacetylation of saturated aliphatic α, ω-diaminomonocarboxylic acid
    CN108623529B|2021-11-26|Preparation method of oxaziclomefone
    Causey et al.1988|A Practical Synthesis of Azetidine
    CN110028409B|2021-11-26|Polysubstituted naphthalene derivative and preparation method thereof
    JP2594826B2|1997-03-26|Method for producing p- or m-hydroxyphenethyl alcohol
    Farrissey Jr et al.1969|Condensation of p-nitrotoluene with aldehydes
    US3833648A|1974-09-03|Process for preparing acylphenoxyaliphatic acid derivatives
    SU1512966A1|1989-10-07|Method of producing 4-|-biphenyl
    SU633481A3|1978-11-15|Method of obtaining 2-thienyl-| ketone
    US4806656A|1989-02-21|Preparation of N-thienyl-chloroacetamides and tetrahydro-thien-3-ylidenimines
    同族专利:
    公开号 | 公开日
    JPS5944294B2|1984-10-29|
    IL49686D0|1976-07-30|
    DE2624360A1|1976-12-16|
    FR2313340B1|1978-11-17|
    CA1075246A|1980-04-08|
    BR7603435A|1977-02-15|
    IE42827B1|1980-10-22|
    FR2313340A1|1976-12-31|
    IE42827L|1976-12-02|
    GB1539733A|1979-01-31|
    TR19245A|1978-08-02|
    BE842177A|1976-11-25|
    DD124378A5|1977-02-16|
    NL7605830A|1976-12-06|
    HU173926B|1979-09-28|
    IL49686A|1979-05-31|
    AU500419B2|1979-05-24|
    NO761850L|1976-12-03|
    ZA763220B|1977-05-25|
    IT1060881B|1982-09-30|
    AU1444476A|1977-12-08|
    SE7606116L|1976-12-03|
    JPS51143638A|1976-12-10|
    CH601155A5|1978-06-30|
    DK238676A|1976-12-03|
    ES448384A1|1977-08-01|
    AR210130A1|1977-06-30|
    LU75055A1|1977-02-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR818032A|1936-02-29|1937-09-16|Geigy Ag J R|Process for the preparation of aldehydes of the series of diaryl or polyaryl ethers|EP0006155A1|1978-06-08|1980-01-09|Ciba-Geigy Ag|3-Phenoxybenzyl amines and 3-benzylbenzyl amines and process for their production|
    GB2185016B|1985-12-20|1989-11-29|Hardwicke Chemical Co|Process for preparing 3-phenoxybenzaldehydes|
    US4691033A|1985-12-20|1987-09-01|Hardwicke Chemical Company|Process for preparing 3-phenoxybenzaldehydes|
    WO2015027067A2|2013-08-23|2015-02-26|Virginia Commonwealth University|Ester nitrates derivatives of aromatic aldehydes with multiple pharmalogic properties to treat sickle cell disease|
    FR3031978B1|2015-01-22|2018-04-20|Centre National De La Recherche Scientifique|PROCESS FOR PRODUCING AN ABLATIVE RESIN|
    FR3031977B1|2015-01-22|2018-04-20|Centre National De La Recherche Scientifique|PROCESS FOR PRODUCING AN ABLATIVE RESIN|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB23770/75A|GB1539733A|1975-06-02|1975-06-02|Preparation of 3-phenoxybenzaldehydes|
    [返回顶部]