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    • 2. 发明授权
    • Process for the preparation of crystalline sodium paraformylphenolate
    • 制备结晶多聚甲酚钠的方法
    • US4346238A
    • 1982-08-24
    • US147678
    • 1980-05-07
    • Alain SchouteetenYani Christidis
    • Alain SchouteetenYani Christidis
    • C07C45/00C07C45/39C07C47/565C07C47/575C07C67/00C07C45/54
    • C07C47/565C07C45/39
    • Sodium paraformylphenolate crystallized with two molecules of water is manufactured by:(a) condensing glyoxylic acid with an excess of phenol in water in the presence of sodium hydroxide at a temperature comprised between 30.degree. C. and 100.degree. C.;(b) neutralizing the solution thus obtained and then freeing it from the unconverted phenol by steam distillation or extraction with a water-immiscible organic solvent and then subjecting it hot under a pressure of oxygen, to a catalytic decarboxylating oxidizing degradation in the presence of sodium hydroxide;(c) allowing the aqueous solution so-obtained, after removal of the catalyst by filtration, and then concentration hot under vacuum to 60% plus or minus 10% of its initial volume, to crystallize; and(d) draining the precipitated crystals, washing them and then drying them to constant weight under vacuum of 1 mm of mercury at 20.degree. C., to obtain sodium paraformylphenolate crystallized with 2 molecules of water or dried to constant weight under a vacuum of 1 mm of mercury at 100.degree. C. to obtain it in anhydrous form. The product is useful for preparing parahydroxy benzaldehyde quantitatively and without other purification reactions.
    • 用两分子水结晶的多聚甲硫醇钠是通过以下方法制造的:(a)在氢氧化钠存在下,在30℃至100℃的温度下,使乙醛酸与过量的苯酚在水中冷凝; (b)中和所得溶液,然后通过水蒸气蒸馏或与水不混溶的有机溶剂萃取,然后将其从未转化的苯酚中释出,然后在氧气压力下热处理,在钠存在下进行催化脱羧氧化降解 氢氧化物; (c)通过过滤除去催化剂后,使真空度为60%±10%,使其结晶,得到如此得到的水溶液。 和(d)排出沉淀的晶体,洗涤,然后在20℃下在1mm汞柱的真空下将其干燥至恒重,得到用2分子水结晶的多聚甲酰基苯酚钠,或在真空下干燥至恒重 在100℃下加入1毫米汞柱,以无水形式得到。 该产品可用于定量和无其他纯化反应制备对羟基苯甲醛。
    • 3. 发明授权
    • Process of preparation of racemic hydroxyarylglycolic acids and novel
products resulting therefrom
    • 制备外消旋羟基芳基乙醇酸及其产生的新产品的方法
    • US4339602A
    • 1982-07-13
    • US243965
    • 1981-02-25
    • Alain SchouteetenYani Christidis
    • Alain SchouteetenYani Christidis
    • C07C59/46C07C51/00C07C51/367C07C59/48C07C65/11C07C59/50
    • C07C51/367
    • The invention relates to a process of preparation of racemic hydroxyarylglycolic acids and the novel products resulting therefrom.According to such process glyoxylic acid is condensed in water in the presence of an alkaline agent at a temperature of between 35.degree. and 100.degree. C., on an excess, or not, of phenolic aromative derivative other than phenol, having at least one proton on either of the ortho or para positions with respect to the phenol function.Application to the production of novel acids such as 4-hydroxy 3-tertiobutyl mandelic acid, 2-hydroxy 5-tertiobutyl mandelic acid, 3-chloro 4-hydroxy mandelic acid, 2-fluoro 4-hydroxy mandelic acid, monohydrated 3,5-dimethoxy 4-hydroxy mandelic acid, 2-hydroxy 5-methyl mandelic acid, (1-hydroxy 2-naphthyl) glycolic acid, 4-ethyl 2-hydroxy mandelic acid, and 4-hydroxy 3-methyl mandelic acid.
    • PCT No.PCT / FR80 / 00126 Sec。 371日期:1981年2月25日 102(e)日期1981年2月25日PCT提交1980年7月24日PCT公布。 公开号WO81 / 00254 日本2月5日,1981年。本发明涉及外消旋羟基芳基乙醇酸的制备方法和由此产生的新产物。 根据这种方法,乙醛酸在碱性试剂存在下,在35℃至100℃的温度下,在除苯酚以外的酚类芳族衍生物的过量或不存在下,在水中冷凝,其具有至少一个质子 在相对于酚官能团的邻位或对位。 适用于生产新型酸如4-羟基-3-叔丁基扁桃酸,2-羟基5-叔丁基扁桃酸,3-氯-4-羟基扁桃酸,2-氟4-羟基扁桃酸,一水合3,5-二 二羟甲基4-羟基扁桃酸,2-羟基-5-甲基扁桃酸,(1-羟基2-萘基)乙醇酸,4-乙基2-羟基扁桃酸和4-羟基3-甲基扁桃酸。
    • 4. 发明授权
    • Process for manufacturing N-acyl derivatives of glycines
.alpha.-substituted by radicals of aromatic nature and novel products
thereof
    • 用于制备由芳香族自由基取代的甘氨酸N-酰基衍生物的方法及其新产物
    • US4088657A
    • 1978-05-09
    • US722286
    • 1976-09-10
    • Yani ChristidisAlain Schouteeten
    • Yani ChristidisAlain Schouteeten
    • C07D333/24C07C67/00C07C231/00C07C231/06C07C231/08C07C231/12C07C233/45C07C233/47C07C233/49C07C101/42
    • C07C233/45
    • This is an improved process of manufacturing N-acyl derivatives of glycines .alpha.-substituted by radicals with an aromatic nature by condensation of the addition product of glyoxylic acid and an amide, with an aromatic compound. In a first stage, the reaction is carried out at low temperature, in a concentrated sulfuric medium, of an aliphatic nitrile of the formula R--C.tbd.N in which R is a radical selected from the group of substituted and unsubstituted, saturated and unsaturated alkyl radicals, with a concentrated aqueous solution of glyoxylic acid. Then in a second stage, the mixture obtained is condensed also at low temperature with a compound of aromatic nature not including a hydroxyl group and having at least one substitutable free hydrogen, and the resulting product is collected. The concentrated sulfuric acid may be supplemented with acetic acid during the second stage. A surface active agent may be also added in this stage. The products are valuable intermediates for the preparation of semi-synthetic penicillins.
    • 这是通过将乙醛酸和酰胺的加成产物与芳族化合物缩合制备具有芳香性的基团被α-取代的甘氨酸的N-酰基衍生物的改进方法。 在第一阶段中,反应在低浓度的硫酸介质中进行,其中R为选自取代和未取代的饱和和不饱和烷基的基团的式RC 3BOND N的脂族腈 ,用浓缩的乙醛酸水溶液。 然后在第二阶段中,所获得的混合物也在低温下与芳族性质不包含羟基并具有至少一个可取代的游离氢的化合物一起冷凝,并收集所得产物。 浓硫酸在第二阶段可补充乙酸。 在该阶段也可以加入表面活性剂。 该产品是制备半合成青霉素的有价值的中间体。