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    • 1. 发明授权
    • Process for the preparation of hydrazones
    • 制备腙的方法
    • US3943132A
    • 1976-03-09
    • US406467
    • 1973-10-15
    • Jean-Pierre SchirmannHenri MathaisPierre TellierFrancis Weiss
    • Jean-Pierre SchirmannHenri MathaisPierre TellierFrancis Weiss
    • C07D213/77C07B43/00C07C20060101C07C67/00C07C241/00C07C251/76C07C251/82C07C251/84C07C251/86C07D20060101C07C109/14C07C109/16C07C109/18
    • C07C249/16C07C251/76C07C251/84
    • This invention relates to a method of preparing hydrazones of the formula ##EQU1## in which R.sub.1 and R.sub.2, which may be identical or different, represent a linear alkyl radical of from 1 to 12 carbon atoms, a branched alkyl or cycloalkyl radical of from 3 to 12 carbon atoms, an aromatic radical of from 6 to 12 carbon atoms having a benzene or naphthalene nucleus, or a radical of from 5 to 12 carbon atoms having a pyridine nucleus, or R.sub.1 and R.sub.2 together form a linear or branched alkylene radical of from 3 to 12 carbon atoms in which one of the carbon atoms of the chain may be replaced by an oxygen atom, all of the above radicals being unsubstituted or substituted by one or more atoms or groups such as chlorine, bromine, fluorine, or iodine atoms or hydroxy, ether, carboxylic acid, carboxylic amide or ester, nitrile, nitro, or sulphonic acid or amide groups, or one of the two radicals R.sub.1 and R.sub.2 may be a hydrogen atom, and in which R.sub.3 and R.sub.4, which may be identical or different, represent a hydrogen atom, a linear alkyl or cycloalkyl radical of from 3 to 12 carbon atoms, in which one of the carbon atoms of the cycloalkyl radical may be replaced by an oxygen atom, or an aromatic hydrocarbon radical of from 6 to 12 carbon atoms or R.sub.3 and R.sub.4 together represent a linear or branched alkylene radical of from 3 to 11 carbon atoms, the above radicals being unsubstituted or substituted by atoms or groups such as chlorine, bromine, fluorine, ethylenic groups, nitro, hydroxy, alkoxy, or carboxylic acid or ester radicals , which comprises reacting a primary or secondary amine of the formulaWherein R.sub.1 and R.sub.2 are as defined above, ammonia, and a carbonyl compound of the formulaWherein R.sub.3 and R.sub.4 are as defined above, with a peroxide compound.
    • 本发明涉及制备式R 1 R 3 ANGLE NN = C ANGLE(I)R 2 R 4的腙的方法,其中可以相同或不同的R 1和R 2表示1至12个碳原子的直链烷基,支链 具有3至12个碳原子的烷基或环烷基,具有苯或萘核的6至12个碳原子的芳族基团或具有吡啶核的5至12个碳原子的基团,或者R 1和R 2一起形成 具有3至12个碳原子的直链或支链亚烷基,其中链中的一个碳原子可以被氧原子代替,所有上述基团都是未取代的或被一个或多个原子或基团取代,例如氯 ,溴,氟或碘原子或羟基,醚,羧酸,羧酰胺或酯,腈,硝基或磺酸或酰胺基,或两个基团R 1和R 2之一可以是氢原子,其中 R3和R4可以相同或相同 不同的是氢原子,具有3-12个碳原子的直链烷基或环烷基,其中环烷基的一个碳原子可以被氧原子取代,或6-12的芳族烃基 碳原子或R3和R4一起表示具有3至11个碳原子的直链或支链亚烷基,上述基团是未取代的或被诸如氯,溴,氟,烯基,硝基,羟基,烷氧基, 或羧酸或酯基,其包括使式WHEREIN R 1和R 2如上所定义的伯胺或仲胺与氨过氧化合物与式WHEREIN R 3和R 4如上定义的羰基化合物反应。
    • 2. 发明授权
    • Method for preparing azines
    • 制备吖嗪的方法
    • US3959262A
    • 1976-05-25
    • US290507
    • 1972-09-20
    • Henri MathaisJean-Pierre SchirmannPierre TellierFrancis Weiss
    • Henri MathaisJean-Pierre SchirmannPierre TellierFrancis Weiss
    • C07C251/88C07C20060101C07C67/00C07C241/00C07C119/00
    • C07C251/88
    • A method is disclosed for preparing symmetrical azines of the formulas ##EQU1## and unsymmetrical azines of the formulas ##EQU2## and mixtures of azines (I), (II) and (IV) and (I), (III) and (V), wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each is a hydrogen atom, a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical or unsubstituted or alkyl substituted cycloalkyl radical of from 3 to 12 carbon atoms, a hydrocarbon radical of from 6 to 12 carbon atoms containing a benzene ring; further provided that R.sup.1 and R.sup.2 can be the same or different radicals, R.sup.3 is a radical different from R.sup.1 and R.sup.2 and R.sup.3 and R.sup.4 are radicals different from each other and each are different from R.sup.1 and R.sup.2 ; or R.sup.1 and R.sup.2 or R.sup.1 and R.sup.3 or R.sup.3 and R.sup.4 bonded to the same carbon atom together form an unsubstituted or aliphatic substituted alkylene radical of from 3 to 11 carbon atoms, each of the aforesaid radicals being unsubstituted or substituted with one or more radicals which are stable in the medium in which the azines are produced.The method comprises reacting in the liquid phase, ammonia with a percarboxylic acid of the formula ##EQU3## wherein R.sup.5 represents a hydrogen atom, a straight chain alkyl radical of from 1 to 18 carbon atoms, a branched chain alkyl radical or unsubstituted or alkyl substituted cycloalkyl radical of from 3 to 12 carbon atoms, a hydrocarbon radical of from 6 to 12 carbon atoms containing a benzene ring, further provided that the aforesaid radicals can contain a non-epoxidizable or epoxidizable ethylenic double bond and/or one or more radicals which are stable in the medium in which the azines are produced, in the presence of a carbonyl compound of the formula ##EQU4## alone or together with a different carbonyl compound ##EQU5## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each have the same meaning defined above and recovering the azine or mixture of azines from the reaction medium.
    • 公开了一种用于制备式R1R1的对称吖嗪的方法。方法C = NN = C ANGLE(I)R2R2 R1R1角度C = NN = C角度(II)R3R3 R3R3角度C = NN = C角度(III)R4R4和不对称吖嗪 式(I),(II)和(IV)和(I),(III)的混合物,其中R 1,R 2,R 3,R 3,R 3, 和(V),其中R 1,R 2,R 3和R 4各自为氢原子,具有1至12个碳原子的直链烷基,支链烷基或未取代的或烷基取代的3至12个碳原子的环烷基 原子,含有苯环的6-12个碳原子的烃基; 进一步提供R1和R2可以相同或不同的基团,R3是不同于R1和R2的基团,R3和R4是彼此不同的基团,并且各自不同于R1和R2; 或者R 1和R 2或R 1,R 3或R 3或R 4和R 4与R 4相同的碳原子一起形成未取代的或脂族取代的3-11个碳原子的亚烷基,上述每个基团是未取代的或被一个或多个基团取代, 在其中产生吖嗪的培养基中是稳定的。
    • 3. 发明授权
    • Method for preparing azines
    • US3951964A
    • 1976-04-20
    • US308836
    • 1972-11-22
    • Pierre TellierHenri MathaisJean-Pierre SchirmannFrancis Weiss
    • Pierre TellierHenri MathaisJean-Pierre SchirmannFrancis Weiss
    • C07C251/88C07C20060101C07C67/00C07C241/00C07C119/00
    • C07C251/88
    • A method is disclosed for preparing symmetrical azines of the formulas ##EQU1## and unsymmetrical azines of the formulas ##EQU2## and mixtures of azines (I), (II) and (IV) and (I), (III) and (V), wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each is a hydrogen atom, a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical or unsubstituted or alkyl substituted cycloalkyl radical of from 3 to 12 carbon atoms, a hydrocarbon radical of from 6 to 12 carbon atoms containing a benzene ring; further provided that R.sup.1 and R.sup.2 can be the same or different radicals, R.sup.3 is a radical different from R.sup.1 and R.sup.2 and R.sup.3 and R.sup.4 are radicals different from each other and each are different from R.sup.1 and R.sup.2 ; or R.sup.1 and R.sup.2 or R.sup.1 and R.sup.3 or R.sup.3 and R.sup.4 bonded to the same carbon atom together form an unsubstituted or aliphatic substituted alkylene radical of from 3 to 11 carbon atoms, each of the aforesaid radicals being unsubstituted or substituted with one or more radicals which are stable in the medium in which the azines are produced.The method comprises reacting ammonia and a carbonyl compound of the formula ##EQU3## alone or together with a different carbonyl compound ##EQU4## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each have the same meaning defined above with at least one diacyl peroxide (acyl peroxide) which are compounds having one or several groups of the structure ##EQU5## and recovering the azine or mixture of azines from the reaction medium.
    • 4. 发明授权
    • Method for preparing azines
    • 制备吖嗪的方法
    • US3943152A
    • 1976-03-09
    • US341057
    • 1973-03-14
    • Pierre TellierJean-Pierre SchirmannHenri MathaisFrancis Weiss
    • Pierre TellierJean-Pierre SchirmannHenri MathaisFrancis Weiss
    • C07C251/88C07C20060101C07C67/00C07C241/00C07C109/14C07C109/16
    • C07C251/88
    • A method is disclosed for preparing symmetrical azines of the formulas ##EQU1## and unsymmetrical azines of the formulas ##EQU2## and mixtures of azines (I), (II) and (IV) and (I), (III) and (V) wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each is a hydrogen atom, a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical or unsubstituted or alkyl substituted cycloalkyl radical of from 3 to 12 carbon atoms, a hydrocarbon radical of from 6 to 12 carbon atoms containing an aromatic nucleus; further provided that R.sup.1 and R.sup.2 can be the same or different radicals, and R.sup.3 and R.sup.4 are the same or different radicals and each are different from R.sup.1 and R.sup.2 ; or R.sup.1 and R.sup.2 or R.sup.1 and R.sup.3 or R.sup.3 and R.sup.4 bonded to the same carbon atom together form an unsubstituted or aliphatic substituted alkylene radical of from 3 to 11 carbon atoms, each of the aforesaid radicals being unsubstituted or substituted with one or more radicals which are stable in the medium in which the azines are produced.The method comprises reacting ammonia, hydrogen peroxide and a carbonyl compound of the formula ##EQU3## alone or together with a different carbonyl compound ##EQU4## or ##EQU5## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each have the same meaning defined above in the presence of an amide or an imide of a carboxylic acid having an ionization constant greater than 5 .times. 10.sup..sup.-5 or of a di-, tri- or tetra-carboxylic acid of which at least one of the carboxylic acid functions has an ionization constant greater than 5 .times. 10.sup..sup.-5 (corresponding to a pK less than about 4.3) to produce the azine or mixture of azines.
    • 公开了一种用于制备式R1R1的对称吖嗪的方法。方法C = NN = C ANGLE(I)R2R2 R1R1角度C = NN = C角度(II)R3R3 R3R3角度C = NN = C角度(III)R4R4和不对称吖嗪 式(I),(II)和(IV)和(I),(III)的混合物,其中R 1,R 2,R 3,R 3,R 3, 和(V)其中R 1,R 2,R 3和R 4各自为氢原子,具有1至12个碳原子的直链烷基,支链烷基或未取代或具有3至12个碳原子的烷基取代的环烷基 含有6至12个碳原子的烃基含有芳香核; 进一步提供R1和R2可以相同或不同的基团,并且R3和R4是相同或不同的基团,并且各自不同于R1和R2; 或者R 1和R 2或R 1,R 3或R 3或R 4和R 4与R 4相同的碳原子一起形成未取代的或脂族取代的3-11个碳原子的亚烷基,上述每个基团是未取代的或被一个或多个基团取代, 在其中产生吖嗪的培养基中是稳定的。
    • 7. 发明授权
    • Process for the preparation of hydrazine compounds
    • US3978049A
    • 1976-08-31
    • US433710
    • 1974-01-16
    • Jean-Pierre SchirmannPierre TellierHenri MathaisFrancis Weiss
    • Jean-Pierre SchirmannPierre TellierHenri MathaisFrancis Weiss
    • C07D213/42B01J21/00B01J23/00C07B43/00C07B61/00C07C20060101C07C67/00C07C241/00C07C251/76C07C251/82C07C251/84C07C251/86C07C251/88C07D213/53C07C109/00
    • C07C251/88C07C249/16
    • This invention relates to a method for preparing an azine of the formula ##EQU1## wherein R.sub.1 and R.sub.2, which may be the same or different, represent a hydrogen atom or a straight alkyl radical of from 1 to 12 carbon atoms, a branched alkyl or cycloalkyl radical of 3 to 12 carbon atoms, or a hydrocarbon radical of from 6 to 12 carbon atoms containing a benzene, naphthalene, or pyridine aromatic ring or R.sub.1 and R.sub.2 together form a straight or branched alkylene radical of 3 to 11 carbon atoms, one of which may be replaced by an oxygen atom, all of the above being unsubstituted or substituted with chlorine, bromine, or fluorine atoms, or ethylene, nitro, hydroxy, alkoxy, carboxylic or percarboxylic acid, amide, nitrile, or carboxylic ester groups, or a mixture of an azine of formula (I) and a hydrazone of the formula ##EQU2## wherein R.sub.1 and R.sub.2 are as defined above and R.sub.3 and R.sub.4, which may be the same or different, represent a straight alkyl radical of from 1 to 12 carbon atoms, a branched alkyl or cycloalkyl radical of 3 to 12 carbon atoms, or a hydrocarbon radical of from 6 to 12 carbon atoms containing a benzene, naphthalene, or pyridine aromatic ring or R.sub.1 and R.sub.2 together form a straight or branched alkylene radical of 3 to 11 carbon atoms, one of which may be replaced by an oxygen atom, all of the above being unsubstituted or substituted by chlorine, bromine, fluorine, or iodine atoms, or hydroxy, ether oxide, carboxylic acid, carboxylic ester, nitrile, nitro, or sulphonic acid or amide groups or one of the two radicals R.sub.3 and R.sub.4 can represent a hydrogen atom, which comprises reacting hydrogen peroxide with ammonia or with a mixture of ammonia and primary or secondary amine of the formula ##EQU3## wherein R.sub.3 and R.sub.4 are as defined above, in the presence of a carbonyl compound of the formula ##EQU4## wherein R.sub.1 and R.sub.2 are as defined above, and a catalyst containing selenium.
    • 8. 发明授权
    • Method for preparing hydrazo-bis-acetonitriles
    • 制备双氢 - 二乙腈的方法
    • US3984451A
    • 1976-10-05
    • US579548
    • 1975-05-21
    • Francis WeissJean-Pierre Schirmann
    • Francis WeissJean-Pierre Schirmann
    • C07C255/66C07C120/00
    • C07C251/88C07C255/00
    • This invention relates to a method for preparing hydrazo-bis-acetonitriles of the general formula: ##EQU1## wherein R.sub.1 and R.sub.2 have the same meaning hereinafter given, which comprises:A. i. reacting a carbonyl compound of the general formula: ##EQU2## wherein R.sub.1 and R.sub.2 have the same meaning hereinafter given, with ammonia and hydrogen peroxide in the presence of cyanogen or a nitrile of the formulaR.sub.3 (CN).sub.n (III)wherein n is an integer from 1 to 6 and R.sub.3 is an unsubstituted or substituted saturated aliphatic, acyclic or cyclic radical of from 1 to 12 carbon atoms or a benzenyl or pyridinyl radical, to form a symmetrical azine of the formula ##EQU3## ii. oxidizing a secondary alcohol of ##EQU4## wherein R.sub.1 and R.sub.2 have the same meaning hereinafter given, at a temperature and pressure which is sufficient to maintain the alcohol in the liquid phase and result in a liquid phase mixture containing the peroxidic products of the auto-oxidation of the alcohol [v] and reacting auto-oxidation products with ammonia and cyanogen or the nitrile R.sub.3 (CN).sub.n of formula (III) to form the symmetrical azine of formula (IV)b. eliminating unreacted ammonia from the medium resulting from (a);C. reacting the azine of formula (IV) contained in the ammonia-free medium resulting from (b) with at least two moles of hydrocyanic acid per mole of azine; andD. recovering the hydrazo-bis-acetonitrile of formula (I).
    • 本发明涉及通式为R1R1 || NC-C-NH-NH-C-CN(Ⅰ)| R2R2的双氢 - 二乙腈制备方法,其中R1和R2具有以下相同的含义, 包含:
    • 9. 发明授权
    • Process for the preparation of symmetrical and unsymmetrical azines and
mixtures thereof
    • 制备对称和不对称吖嗪及其混合物的方法
    • US3972876A
    • 1976-08-03
    • US532650
    • 1974-12-13
    • Jean-Pierre SchirmannFrancis Weiss
    • Jean-Pierre SchirmannFrancis Weiss
    • C07C249/02C01B21/16C07C20060101C07C251/88C07C255/45C07C109/00
    • C07C251/88
    • A process is disclosed for the preparation of symmetrical azines of the formulas ##EQU1## and unsymmetrical azines of the formulas ##EQU2## and mixtures of azines (I), (II), and (IV), and (I), (III) and (V), wherein R.sup.1 , R.sup.2, R.sup.3 and R.sup.4 each is hydrogen, a straight-chain alkyl radical of from 1 to 12 carbon atoms, a branched-chain alkyl radical or a cycloalkyl radical of from 3 to 12 carbon atoms or a phenyl radical, the aforesaid radicals being unsubstituted or substituted with a radical which is stable in the medium in which said azines are produced; and in which case R.sup.1 and R.sup.2 can be the same or different radicals, R.sup.3 is a radical different from R.sup.1 and R.sup.2, R.sup.3 and R.sup. 4 are radicals different from each other, and each are different radicals from R.sup.1 and R.sup.2 ; or R.sup.1 and R.sup.2 or R.sup.1 and R.sup.3, or R.sup. 3 and R.sup.4 of either or both the >C=N-- moieties together form a cyclic or substituted cyclic radicals of from 3 to 11 carbon atoms in the ring.
    • 公开了用于制备式R1R1的对称吖嗪的方法。R1 = NN = C ANGLE(I)R2R2 R1R1角度C = NN = C角度(II)R3R3 R3R3角度C = NN = C角度(III)R4R4和 (I),(II)和(IV)和(I)的混合物,其中R 1,R 2,R 3,R 3,R 4, ,(III)和(V),其中R 1,R 2,R 3和R 4各自为氢,具有1至12个碳原子的直链烷基,支链烷基或环烷基为3至12 碳原子或苯基,上述基团是未被取代的或被在所述制备所述吖嗪的介质中稳定的基团取代; 在这种情况下,R 1和R 2可以是相同或不同的基团,R 3是不同于R 1和R 2的基团,R 3和R 4是彼此不同的基团,并且各自是不同的R 1和R 2基团; 或者R 1和R 2或R 1和R 3或R 3和R 4中的任一个或两个> C = N-部分一起形成环中具有3至11个碳原子的环状或取代的环状基团。
    • 10. 发明授权
    • Method for preparing symmetrical and unsymmetrical ketazines and
mixtures thereof
    • 制备对称和不对称的喹的方法及其混合物
    • US3972874A
    • 1976-08-03
    • US531058
    • 1974-12-09
    • Henri MathaisJean-Pierre SchirmannFrancis Weiss
    • Henri MathaisJean-Pierre SchirmannFrancis Weiss
    • C07C109/00
    • C07C251/88
    • The invention relates to a method for preparing symmetrical ketazines of the formula ##EQU1## and unsymmetrical ketazines of the formula ##EQU2## and mixtures of ketazines (I), (II) and (IV) and (I), (III) and (V) wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical or cycloalkyl radical of from 3 to 12 carbon atoms, or a phenyl radical, the aforesaid radicals being unsubstituted or substituted with radicals which are stable in the medium in which the ketazines are prepared; and in which case R.sup.1 and R.sup.2 can be the same or different radicals, and R.sup.3 and R.sup.4 are radicals different from each other and are each a radical different from R.sup.1 and R.sup.2 ; or R.sup.1 and R.sup.2, or R.sup.1 and R.sup.3, or R.sup.3 and R.sup.4 of either or both the ##EQU3## moieties together form a cyclic or substituted cyclic radical of from 3 to 11 carbon atoms in the ring, which comprises:A. oxidizing a secondary alcohol of the formula ##EQU4## alone or together with a different secondary alcohol of the formula ##EQU5## or ##EQU6## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each has the same meaning as defined above, the oxidation to be carried out in the liquid phase employing molecular oxygen or a gaseous mixture containing the same, at a temperature and pressure which is sufficient to maintain the alcohol or alcohols in the liquid phase and result in a liquid phase mixture containing the peroxidic products of the auto-oxidation of the alcohol (VI) or the alcohols (VI) and (VII) or (VI) and (VIII);b. reacting the peroxidic products with ammonia in the presence of cyanogen or a nitrile R.sup.5 (CN).sub.n (IX) wherein n is an integer of from 1 to 6 and R.sup.5 is an unsubstituted or substituted saturated aliphatic, acyclic, or cyclic radical of from 1 to 12 carbon atoms or a phenyl or pyridinyl radical to result in the ketazine (I) or the mixture of ketazines (I), (II) and (IV) or (I), (III) and (V); andC. recovering the ketazine or mixture of ketazines.
    • 本发明涉及一种制备式R1R1对称的嗪酮的方法。方法C = NN = C ANGLE(I)R2R2 R1R1角度C = NN = C角度(II)R3R3 R3R3角度C = NN = C角度(III)R4R4和 式(R1)的非对称性的喹诺酮C = NN = C角度(IV)R2R3 R1R3角C = NN = C角(V)R2R4以及它们的混合物(I),(II)和(IV)和(I) III)和(V)其中R 1,R 2,R 3和R 4各自为具有1至12个碳原子的直链烷基,具有3至12个碳原子的支链烷基或环烷基,或苯基, 上述基团是未取代的或被其中制备该酮的培养基中稳定的基团取代; 并且在这种情况下,R 1和R 2可以是相同或不同的基团,并且R 3和R 4是彼此不同的基团,并且各自是与R 1和R 2不同的基团。 或R 1和R 2,或R 1和R 3,或任意一个或两个ANGLE C = N-部分的R 3和R 4一起形成在环中具有3至11个碳原子的环状或取代的环状基团,其包括: