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    • 4. 发明授权
    • Process for the preparation of cephalosporins intermediates
    • 制备头孢菌素中间体的方法
    • US5387679A
    • 1995-02-07
    • US988961
    • 1993-03-15
    • Loris SogliDaniele TerrassanGiuseppe Ribaldone
    • Loris SogliDaniele TerrassanGiuseppe Ribaldone
    • C07D501/00C07D501/04C07D501/18C07D501/26C07D501/36A61K31/545
    • C07D501/00Y02P20/55
    • The present invention relates to a process for preparing a compound of formula (I) ##STR1## wherein R is an heterocyclic group which contains at least one nitrogen atom with or without oxygen or sulphur and R.sup.1 and R.sup.2 are both hydrogen atoms or one of them is an hydrogen atom and the other is an acyl group; the process comprising reacting a compound of formula (II) ##STR2## wherein R.sup.1 and R.sup.2 are each as defined above, and wherein, if necessary, any reactive group is protected by a suitable protective group, or a salt thereof, with a compound of formula (III)R--SH (III)wherein R is as defined above, or a salt thereof, in the presence of an acid and of a compound of formula (IV) ##STR3## wherein each of R.sup.3 and R.sup.4 is a C.sub.1 -C.sub.4 alkyl group or R.sup.3 and R.sup.4 taken together are a C.sub.2 or C.sub.3 alkylene chain and, if necessary, removing the protective groups possibly present.The compounds of formula (I) are useful intermediates in the synthesis of Cefazolin and Cefazedone.
    • PCT No.PCT / EP92 / 01595 Sec。 371日期1993年3月15日 102(e)1993年3月15日PCT提交1992年7月14日PCT公布。 出版物WO93 / 02085 本发明涉及一种制备式(I)化合物的方法,其中含有或不具有氧或硫的至少一个氮原子,且R 1和R 2均为氢原子或其中之一 是氢原子,另一个是酰基; 该方法包括使式(II)化合物其中R 1和R 2各自如上所定义,并且其中如有必要,任何反应性基团被合适的保护基或其盐保护,其中 式(III)化合物其中R如上定义的R-SH(III)或其盐在酸和式(IV)化合物的存在下,其中R 3 并且R 4是C 1 -C 4烷基或R 3和R 4一起是C 2或C 3亚烷基链,并且如果需要,除去可能存在的保护基团。 式(I)化合物是合成头孢唑啉和头孢唑酮的有用中间体。
    • 6. 发明授权
    • Preparation of pyrazine derivatives
    • 吡嗪衍生物的制备
    • US4511718A
    • 1985-04-16
    • US471691
    • 1983-03-03
    • Giuseppe RibaldoneMaria G. FelicioliClaudio SantiniGiovanni Agnes
    • Giuseppe RibaldoneMaria G. FelicioliClaudio SantiniGiovanni Agnes
    • C07D241/14C07D241/12C07D241/24C07D401/02C07D413/02C07D417/02
    • C07D241/12C07D241/24
    • A process for the preparation of a pyrazine derivative of the formula ##STR1## wherein R.sub.1 represents hydroxy, C.sub.1 -C.sub.6 alkoxy, or a group of the formula NR.sub.2 R.sub.3 in which R.sub.2 and R.sub.3 are independently a hydrogen atom or C.sub.1 -C.sub.6 alkyl or, together with the nitrogen atom to which they are linked, form a saturated ring having five or six atoms which may contain one or more additional heteroatoms; which process comprises reacting a compound of the formula: ##STR2## wherein R represents a hydrogen atom, C.sub.1 -C.sub.6 alkyl, or C.sub.1 -C.sub.6 alkoxy, Y represents a hydrogen atom or a sodium, lithium, or potassium ion, and A is a nitrile group or a substituent of the formula COR.sub.1 where R.sub.1 is as defined above either with pyruvic aldehyde oxime of the formula: ##STR3## or with a pyruvic aldehyde oxime acetal derivative of the formula: ##STR4## wherein R.sub.4 and R.sub.5 are independently a hydrogen atom or C.sub.1 -C.sub.6 alkyl or may be linked together so that the compound of formula IV is a cyclic acetal; and, when A is a nitrile group, hydrolyzing the reaction product.
    • 制备式I的吡嗪衍生物的方法,其中R 1表示羟基,C 1 -C 6烷氧基或式NR 2 R 3基团,其中R 2和R 3独立地为氢原子或C 1 -C 6烷基, 与它们所连接的氮原子一起形成具有五个或六个原子的饱和环,其可以含有一个或多个另外的杂原子; 该方法包括使下式化合物:其中R表示氢原子,C1-C6烷基或C1-C6烷氧基,Y表示氢原子或钠,锂或钾离子,A为 腈基或式COR1的取代基,其中R 1如上所定义,与下式的丙酮酸肟或与下式的其中R 4和R 5为的丙酮酸肟缩醛衍生物 独立地是氢原子或C 1 -C 6烷基或可以连接在一起,使得式Ⅳ化合物是环状缩醛; 并且当A为腈基时,水解反应产物。
    • 7. 发明授权
    • Anthraquinone compounds and process for preparing same
    • 蒽醌化合物及其制备方法
    • US4098793A
    • 1978-07-04
    • US836087
    • 1977-09-23
    • Giuseppe RibaldoneRenato GrecuCamillo PaffoniGiuseppe Sironi
    • Giuseppe RibaldoneRenato GrecuCamillo PaffoniGiuseppe Sironi
    • C09B1/44C09B1/516C09B1/54D06P1/24C07D285/10
    • D06P1/24C09B1/44C09B1/516C09B1/542
    • The present invention relates to a new class of compounds belonging to the anthraquinone series, having the general formula: ##STR1## wherein R, R', R", R'", R' are indifferently H or Chlorine, ##STR2## Such compounds exhibit a color varying from yellow to violet depending on the nature and position of substituents R, R', R", R'", R'.sup.v and, in virtue of their excellent stability characteristics, they are particularly useful as pigments and vat dyes.This invention relates furthermore to the preparation of compounds having general formula (I) and to the utilization thereof, particularly in the following applications:Pigmentation of plastic materials, such as polyvinyl chloride, polystyrene, polyolefins, polymethylmethacrylate, polycarbonates and ABS copolymers (acrylonitrile-butadiene-styrene);Pigmentation of varnishes, stoving enamels, inks and pastes for the printing of textiles;Vat dyeing of cellulose fibres such as cotton, flax, rayon.BACKGROUND OF THE INVENTIONAs far as it is known, the anthraquinone derivatives of 1,2,5-thiadiazole-3,4-dicarboxylic acid of formula (I), which are the object of the present invention, are not described in the Art.The prior Art, however not directly pertinent, generically describes dyestuffs of the anthraquinone series deriving from dicarboxylic acids, for example benzenic, pyridinic, aliphatic acids etc.OBJECTS OF THE INVENTIONIt is an object of this invention to provide a new class of anthraquinone compounds of general formula (I), having useful applications in the field of the pigments and of the vat dyes. Another object is to provide a process for preparing same.GENERAL DESCRIPTION OF THE INVENTIONThese and still other objects, that will more clearly appear to those skilled in the Art from the following description, are achieved by compounds having general formula (I), prepared by means of a process characterized in that the dichloride of 1,2,5-thiadiazole-3,4-dicarboxylic acid (II) is reacted with 1-aminoanthraquinone or substituted derivatives (III) thereof according to a substantially stoichiometric molar ratio, in the presence of an inert solvent, at a temperature ranging from 100.degree. to about 170.degree. C.The reaction can be schematically represented by the following equation (1): ##STR3## wherein R', R", R'", R'.sup.v have the meaning already specified; HCl forms and liberates as a gas from the reacting mixture. It is not necessary, therefore, to employ basic substances to neutralize hydrochloric acid. As mentioned hereinbefore, the reaction is conducted in an inert solvent and at a temperature comprised between 100.degree. and about 170.degree. C, preferably between 120.degree. and about 150.degree. C.1-aminoanthraquinones (III) employable in the present invention are in particular:1-aminoanthraquinone, 1-amino-4-hydroxyanthraquinone, 1-amino-4-benzamidoanthraquinone, 1-amino-5-benzamidoanthraquinone, 1-amino-4-(p-acetamidoanilino)-anthraquinone, 1-amino-4-(p-toluidino)-anthraquinone, 1-amino-5-methoxyanthraquinone, 1-amino-2-phenoxy-4-hydroxyanthraquinone, 1-amino-2,4-dibromoanthraquinone, 1-amino-2-bromo-4-hydroxyanthraquinone, 1-amino-6,7-dichloroanthraquinone etc.As inert solvent it is possible to use chlorobenzene, the various dichlorobenzenes and trichlorobenzenes, and nitrobenzenes.The time required for the reaction varies from 2 to 8 hours, depending on the reaction temperature and on the type of 1-aminoanthraquinones utilized. The molar ratio is practically stoichiometric, that is: 2 moles of anthraquinone compound (III) for 1 mole of dichloride (II).The raw materials necessary for the process according to this invention are easily available, as 1-aminoanthraquinone and the substituted derivatives (III) thereof are commercial products usually employed as intermediates for dyestuffs and pigments.As to the dichloride of 1,2,5-thiadiazole-3,4-dicarboxylic acid (II), such product is known since long and is obtained, according to known techniques, by chlorination with SOCl.sub.2 of the monopotassium salt of 1,2,5-thiadiazole-3,4-dicarboxylic acid, that is, in its turn, a known compound.According to an effective embodiment, the present invention is conducted by operating in practice as follows: the dichloride of 1,2,5-thiadiazole-3,4-dicarboxylic acid (II) and the 1-aminoanthraquinone or its substituted derivatives (III) are heated, after mixing in the inert solvent, to 100.degree.-170.degree. C, preferably to 120.degree.-150.degree. C, until the anthraquinone compound (III) has thoroughly disappeared.The thin layer chromatography is useful for this check.At the end of the reaction the reaction mixture is filtered, preferably in hot conditions, and the pigment cake is then washed with the reaction solvent and successively with methanol until the washings result colourless.The pigments obtained according to this invention are substances exhibiting a colour varying from yellow to violet and characterized by a high insolubility in the common organic solvents and by a high melting point, generally higher than 300.degree. C.To impart the particular desired applicative characteristics to the products so obtained it is impossible to utilize the grinding, for example in a ball mill, or the precipitation from sulphuric acid and in general the techniques already known.Also for the dyeing of plastic materials, of varnishing products and for the vat dyeing the pigments of the present invention are consistent with the conventional techniques.Due to the simple preparation conditions and applicative characteristics of the obtained pigments, the present invention appears particularly advantageous.Preparation and application of the present invention will be now described more in detail in the following examples, which are given, however, by way of example only.
    • 本发明涉及一类属于蒽醌系列的化合物,具有以下通式:其中R,R',R“,R”',R'为无差异的H或氯,
    • 8. 发明授权
    • Method for the preparation of the monopotassium salt of
1,2,5-thiadiazol-3,4-dicarboxylic acid, and intermediate product
    • 制备1,2,5-噻二唑-3,4-二羧酸的单钾盐的方法和中间产物
    • US4077966A
    • 1978-03-07
    • US775767
    • 1977-03-09
    • Giuseppe RibaldoneRenato Grecu
    • Giuseppe RibaldoneRenato Grecu
    • C07D285/10
    • C07D285/10
    • Process for the preparation of the monopotassium salt of 1,2,5-thiadiazol-3,4-dicarboxylic acid (I). Involves double-stage saponification of 3,4-dicyano-1,2,5-thiadiazole (II), 3-cyano-4-carbamoyl-1,2,5-thiadiazole (III) is obtained from an aqueous suspension of 3,4-dicyano-1,2,5-thiadiazole (II) by catalytic hydration through the addition of aqueous KOH, desirably at a temperature of from 20.degree. to 50.degree. C. and with a molar ratio of 3,4-dicyano-1,25-thiadiazole (II) to KOH of from 1:0.01 to 1:0.8. This is followed by hydrolysis, by the further addition of aqueous KOH, desirably at a temperature of from 85.degree. to 100.degree. C., until attaining an overall molar ratio of 3,4-dicyano-1,2,5-thiadiazole (II) to KOH of from about 1:2.0 to 1:2.35, a molar ratio of 3,4-dicyano-1,2,5-thiadiazole (II) to H.sub.2 O of from about 1:20 to 1:23. Thereafter, from the resulting solution of dipotassium salt of 1,2,5-thiadiazole-3,4-diccarboxylic acid, the monopotassium salt is separated by acidification of said solution.
    • 制备1,2,5-噻二唑-3,4-二羧酸(I)的单钾盐的方法。 涉及3,4-二氰基-1,2,5-噻二唑(II),3-氰基-4-氨基甲酰基-1,2,5-噻二唑(III)的双级皂化由3, 通过加入KOH水溶液催化水合,优选在20至50℃的温度和摩尔比为3,4-二氰基-1,2-二氰基-1,2,5-噻二唑(II) ,25-噻二唑(II)至KOH的摩尔比为1:0.01至1:0.8。 然后进行水解,通过进一步加入KOH水溶液,期望温度为85℃至100℃,直到达到3,4-二氰基-1,2,5-噻二唑(II)的总摩尔比 )至KOH的摩尔比为约1:2.0至1:2.35,3,4-二氰基-1,2,5-噻二唑(II)与H 2 O的摩尔比为约1:20至1:23。 然后,从得到的1,2,5-噻二唑-3,4-二羧酸的二钾盐溶液中,通过所述溶液的酸化分离单钾盐。