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    • 专利摘要:
    1357811 Azines UGINE KUHLMANN 26 May 1971 [12 June 1970 29 Dec 1970 24 Feb 1971 3 March 1971] 17328/71 Heading C2C Azines R 1 R 2 C=NN=CR 1 R 2 (where R 1 and R 2 are hydrogen or substituted or unsubstituted alkyl or cycloalkyl of up to 12 C or phenyl, or together form a linear or branched C 3-11 alkylene radical) are prepared by reacting ammonia with R 1 COR 2 and H 2 O 2 in the presence of cyanogen or a nitrile R 3 (CN) n (where n is 1-6 and R 3 is an aliphatic or alicyclic hydrocarbon radical or a radical containing a benzene or pyridine ring having up to 12 carbon atoms, and is optionally substituted with 1-6 identical or different groups). Suitable substituents for R 1 and R 2 are Cl, Br, F, NO 2 or OCH 3 ; suitable substituents for R 3 are amide, carboxylic acid, carboxylic ester, nitro, primary, secondary or tertiary amino, amine oxide, F, Cl, Br, I, OH, ether, acetal, epoxy, sulphoxide, sulphide, sulphone or sulphonic acid. Solvents and H 2 O 2 -stabilizing agents may be present, and also a catalyst which is an ammonium or alkali metal salt of a mineral acid, an aliphatic or aromatic carboxylic acid or an alkyl- or arylsulphonic acid having less than 20 carbon atoms.
    公开号:SU959624A3
    申请号:SU711664326
    申请日:1971-06-12
    公开日:1982-09-15
    发明作者:Ширманн Жан-Пьер；Вайс Франсис
    申请人:Южин Кульман (Фирма)；
    IPC主号:
    专利说明:

    (5) METHOD OF OBTAINING AZINS
    . one
    The invention relates to a process for the preparation of azines of the formula 1
    R
    one

    (I)
    C IT-N C

    g
    where one of R and Rj is hydrogen, the other or both R ;, and RU is a linear or branched lower alkyl or 10 phenyl, or R and R 2 are together cycloalkyl with 6-12 carbon atoms, KOToi i.e. are used in different organic syntheses.
    A known method for producing azines, 15 is that chloramine, previously obtained by reacting aqueous hypochlorite with ammonia, is treated with a carbonyl compound of formula It
    Bf CO-R,
    (U)
    and R where is one of R
    hydrogen, other or both
    R and unbranched or branched lower alkyl or feil, or R and R 2. together - cycloalkyl with 6-12 carbon atoms, in the presence of an aqueous solution of ammonia at i 0-55 C in two or more reactors connected in the form of a cascade system
    The disadvantage of this method is the use of chloramine, which requires caution in working with it, the use of a group of reactors and the need to monitor the pH of the medium, which should be in the range of 12.8-13.5. which complicates the whole process.
    The purpose of the invention is to simplify the process.
    This goal is achieved by the fact that according to the method of producing azines of formula 1, ammonia is reacted with a carbonyl compound of formula II and hydrogen peroxide in the presence of a nitrile of formula lit.
    Rf (C1) d. (llf) where n 1-6; R is alkyl unsubstituted or substituted by halogen, hydroxyl groups, amino groups or carboxyl groups with 1-12 carbon atoms, cycloalkyl, phenyl or a pyridine ring substituted by lower alkyl, at O-100 0. Preferably, the process is carried out in the presence of acetic acid as a catalyst or ammonium acetate, and methanol as a solvent. The proposed method for producing azines involves introducing four products into the reaction in aqueous solutions or in the presence of a solvent to facilitate the homogenization of the mixture. The solvent is preferably chosen from alkyl mono alcohols containing from 1 to A carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, isobutanol. The preferred temperature ranges from about to about. Work can be carried out at atmospheric pressure or at pressures up to 10 atm if this is required to maintain ammonia in solution. Reagents can be added in equimuclear amounts, but you can also use a molar deficit or an excess of one or more BOB reactants, for example, 0.2 5 mol of aldehyde or ketone and ammonia per 1 mol of hydrogen peroxide can be used. The nitrile is preferably added in an amount of 1-10 eq of nitrile per 1 mole of H, 0i. Hydrogen peroxide can be used in the form of a 30-90 w / w aqueous solution, ammonia can be used anhydrite or in a common aqueous solution. Reagents can be introduced into the reaction medium at the same time or in any sequence, which, in particular, makes it possible to effectively control the exothermic reaction. It is possible to combine the aldehyde or ketone with hydrogen peroxide in a known manner and introduce such a peroxide into the reaction, it is also possible to separately perform the reaction of the aldehyde or ketone with ammonia prior to the introduction of hydrogen peroxide and nitrile. In addition, amino peroxide can be prepared by reacting an aldehyde or ketone with ammonia and hydrogen peroxide, which then reacts with a nitrile. It may be appropriate to add to the reaction mixture a product that stabilizes hydrogen peroxide, such as phosphoric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid or its sodium salts. The catalyst can be a small amount of ammonium or alkali metal salts, in particular lithium, sodium and potassium, hydrogen acid or inorganic hydroxy acid, aliphatic or aromatic carboxylic acids or alkylarylsulfonic acids containing less than 20 carbon atoms, the anions of which remain static under oxidizing conditions . For example, the following ammonium and alkali metal salts can be used: fluorides, chlorides, sulfates, nitrates, phosphates, pyrophosphates, borates, carbonates, formates, acetates, propionates, biturates, isobutyrates, hexanoates, octanoates, dodecanoates, stearates, oxalates, soucats , glutarates, adipates, benzoates, phthalates, methanesulfonates, ethanesulfonates, benzenesulfonates, p-toluenesulfonates, etc. The amount of catalyst ranges from 0.01 to 2% by weight of the reaction mixture as a whole. Salts can be used on their own, as well as, in the case of ammonium salts, they can be prepared within the medium itself, using the ammonia content in the mixture and adding the appropriate acid. Example 1. A solution of 103 g of benzonitrile (1 mol), 18 g of water, 1 g of disodium salt of ethylene diamine tetraacetic acid and 0.15 g of ammonium acetate in 320 g of methanol are placed in the reactor. Barboterum, 23 g of ammonia gas (1.35 mol) is dissolved, then gradually introduced at 72 g of isobutyraldehyde (1 mol) and separately 28 g of a 61% aqueous solution of hydrogen peroxide (0.5 mol) and allowed to react for fS h at the same temperature. At the end of the reaction, the mixture is quantitatively analyzed. The amount of isobutyraldazine determined by chemical analysis is 23 g (O, 163 mol). Then methanol and unreacted isobutyraldehyde are evaporated under a pressure of 200 mm Hg. The benzamide crystallized is filtered off and the filtrate is extracted with chloroform. The extract is dried over anhydrous sodium sulfate, evaporated, and distilled with isobutyraldazine under a pressure of 20 mm Hg. 11.7 g of product are obtained boiling at 66 ° C and 20 mm Hg. The resulting product is determined with. spectral analysis by IR radiation of the C N band at 1660, it is similar to the product synthesized by the reaction of isobutyraldehyde with hydrazine hydrate. Example 2. The reaction is carried out similarly to Example 1 using 1 acetonitrile (1 mol). The quantitative analysis showed that the mixture contained g of isobutyraldazine (0.07 mol). Example 3. A solution of 51.5 g of benzonitrile (0.5 mol), 18 g of water, 0.5 g of disodium salt of ethylenediaminetetraacetic acid and 0.05 g of acetic acid in TbO g of methanol are placed in the reactor. Barbotiru, dissolve 8.5 g of gaseous ammonia (0.5 mol) and add 29 g of propionaldehyde (0.5 mol), then UH b1 -aqueous solution of hydrogen peroxide (about 25 mol). The reaction was continued for 24 hours at which point, after which 6.7 g of propionald azine (0.0b mol) was added to the mixture. Analogously to Example 1, g of pure propconaldazine boiling at kS C 20 mm Hg is isolated. The IR spectrum (C N band at 1660) is similar to the spectrum of the product obtained from propirnaldehyde and hydrazine hydrate. PRI meri k. The reaction is carried out analogously to example 3, replacing propionaldehyde with 55 g of benzaldehyde (0.5 mol). After 2 hours, 1A, 6 g of benzaldazine (0.07 mol) was added to the mixture. The usual separation step results in 8 g of pure benzaldazine in the form of yellow crystals with m, pl., IR spectrum: C band at 1625 cm. Example 5 20.5 g of acetonitrile (0.5 mol) were added to 160 g of methanol. The mixture is heated to After that, 2k, 3 g of a 70% aqueous hydrogen peroxide solution (0.5 mol) and a mixture of kS g cyclohexanone (0.5 mol), g ammonia (18.8 weight (0.5 mol), 16 g of methanol and 0.5 g of disodium salt of ethylenediaminetetraacetic acid. Reak qi lasts 3 hours. The presence of 33.5 g of cyclohexanonazine (0.175 mol) was determined by gas chromatography, which corresponds to a yield of 35% (to hydrogen peroxide). The solution is then evaporated at a pressure of 200 ml Hg. until the evaporation temperature reaches 50 ° C. The residue is extracted with chloroform. The extract is dried over anhydrous sodium sulphate and distilled. 23 g of pure cyclohexanonazine (0.153 mol) are obtained, boiling at 8788 C and 0.2 mm Hg. and crystallizing upon cooling (F -). IR spectrum of the product: characteristic-; The C N band with a UV spectrum (cyclohexane) has a threshold at 216 m with a threshold at 23 m; The NMR spectrum lies in Ry 0 MHz. It has two peak arrays, centered at 6 1.60 and 2.3 V ppm, and with an intensity ratio of 3/2. PRI me R 6. 73.5 g of cyclohexanone (0.75 mol) /, 7712 benzonitrile benzene (0.75 mol) and g of methanol are mixed. The mixture is saturated at 25 ° C by bubbling ammoniac gas, and 21 G of ammonia (1.25 mol) is absorbed. Then, over a period of 1 hour, 36.5 g of a 70% aqueous solution of H, 0 (0.75 mol) was added. After 2 hours (upon cessation of the additives), a quantitative analysis of the cyclohexanonazine present in the medium is carried out by gas chromatography. Get g (0,258 mol), which corresponds to the output 3 |, with respect to hydrogen peroxide. EXAMPLE 7 Grams of benzonitrile (0.5 mol., 1bO g of methanol) are mixed. 2.3 g (0.5 mol) and a mixture of 9 g of cyclohexanone (0.5 mol) are added at a time for 1 hour, and 45 g of 18.8% ammonia (0.5 mol), 25 g of methanol. After 2.5 hours of reaction (at the end of the addition), the content of cyclohexane-azine (g (0.133 mol)) is quantitatively determined by gas chromatography; corresponds to a yield of 26.6% relative to hydrogen peroxide.) Example 8. BUT g of methanol, 77.3 g of benzonitrile (0.75 mol), + 3.5 g of acetone (0.75 mol of 55.5 g of 23% ammonium ammonium ( 0.75 mol), heated to 0 C and for 1 h water, 3 t; 2 g (75 mol). The mixture was kept at 3 h, then acetonazine contained in the medium was quantitatively determined by gas chromatography (16.5 G (0, mol), corresponds to 19.8% yield relative to hydrogen peroxide.) Example 9. Mix 20.5 g of acetonitrile (0.5 mol), 90 g of 18.8% ammonia (1 mol), 72 g of methyl ethyl ketone (1 mol) and 160 g of methanol. Then, 2C, 3 of a 70% aqueous solution (0.05 mol) are introduced at room temperature for 1 h. After 2 hours of reaction, gas chromatography was carried out to quantitatively determine methyl ethyl ketonazine. 12 g (0.035 mol) are obtained, which corresponds to yield 17 relative to hydrogen peroxide. Example. 10. Mix 20.5 g of acetonitrile (0.5 mol), 90 g of 18 gO ammonia (1 mol), 86 g of pentanone (1 mol), and 1 gO g of methanol. Then, over 1 hour, 2t, 3 g of a 70% solution of 0-2, is added at room temperature. mole). After 2 h of reaction, the presence of 8.7 g of pentanone-2-azine (0.052 mol) in the medium is determined by that gas chromatography.
    Salt
    Example
    Ammonium chloride
    Ammonium Sulphate
    Ammonium nitrate
    Ammonium carbonate
    Bura (Na, 10)
    Monosodium Phosphate
    Ammonium formate
    Ammonium oxalate
    Ammonium n-octanate
    Ammonium benzoate
    Lithium carbonate
    The output of acetone; Amount, relative to g
    .one
    70 68,
    71
    75
    77
    65
    69
    65
    69 55
    55
    权利要求:
    Claims (3)
    [1]
    51 4 Example 11.8 the reactor is injected with a solution of 20.5 g (0.5 mol) of acetonitrile, 58 g (1 mol) of acetone, 18 g (1 mol) of water, 1 g of disodium salt is ethylenediaminetetraacetic acid and 0.15 g of acetic acid ammonium in 100 g (5 mol of methanol. Barbotiro, dissolve, 6 g (0.86 mol) of gaseous ammonia. The mixture is heated to and within 5 min. 19.5 g of 70% aqueous hydrogen peroxide solution (o, 4 mol.) The reaction was continued for 7 hours at the same temperature, ammonia gas was bubbled in at a rate of 1.7 (0.1 mol) per hour. At the end of the reaction, gas chromatography determined t the amount of acetonazine contained in the medium (35.3 g, 0.315 mol, corresponding to a yield of 78.5% relative to hydrogen peroxide). Example 12. The reaction is carried out analogously to example 11, but instead of ammonium acetate, 0.09 g of acetic acid is added to to obtain ammonium acetate in siti. After 7.5 h of reaction, quantitative determination is performed using gas chromatography. 36 g (0.32 mol) of acetonazine are obtained, which corresponds to an 80% yield relative to hydrogen peroxide. Examples The reaction is carried out analogously to example 11, but instead of ammonium acetate, various salts are used. Example 2 - comparative (no added salt). The results obtained are presented in the table. 9E 25. Dissolve 18 g of Example (1 mol) of cyclododecanone, 20.5 g (0.5 mol), acetonitrile, 18 g of water (1 mol), 0.1 g of disodium salt of ethylenediaminetetraacetic acid and .0.1 g of acetic acid acid in 450 g of methanol, then sparging, anhydrous ammonia is added to dissolve 17 g (1 mol) of the reagent. Heated to 50 ° C and 20 g of a 70% aqueous solution of hydrogen peroxide (0, mol) are introduced within 5 minutes. After 2 h of reaction, 18 g (0.605 mol) of cyclodecadec nonazin are determined by gas chromatography which corresponds to a yield of 12.5 relative to hydrogen peroxide. 26 120 Example (1 mol) of acetophenone, 20.5 g (0.5 mol of acetonitrile, 18 g of water (1 mol), 1 g of disodium salt of ethylenediaminetetraacetic acid and 0.15 g of ammonium acetate in 1 кс of g of methanol. Then ammonium gas was introduced into the bubbler until absorbed 16.7 g (0.084 mol). The mixture was heated to 50 ° C and 21.5 70% aqueous hydrogen peroxide solution (o mol) was introduced in 5 minutes. After 1 h of reaction gas chromatography determines the presence of acetophenonazine in the medium of g (o, 61 mol). The yield corresponds to 22.8% relative to hydrogen peroxide. Example 27. A reactor is placed in the reactor Solution containing 20.5 g of acetonitrile (0.5 mol), 58 g of acetone (1 mol), 18 g of water, 1 g of disodium salt, ethylenediaminetetraacetic acid and 0.2 g of ammonium acetate; the mixture is heated to and in it dissolve 2.3 g of ammonia (0.135 mol), an ammonia gas was bubbled through to do this, and then 20.5 g of a b7% aqueous solution of hydrogen peroxide (0.0 mol) were introduced over 2 hours. The reaction was continued at the same temperature for 7 hours, then quantitative analysis of the mixture. Chemical analysis and gas chromatography established the content of acetonazine, 31.4 g (0.28 mol), which corresponds to the yield with respect to hydrogen peroxide. Example 28. A stainless steel autoclave with a capacity of 1 l is loaded with 20.5 g of acetonitrile (0.5 mol), 58 g of acetone (I mol), 1bO g of methac10 Nol and a solution of 1.2 g of ethylenediaminetetraacetic acid disodium salt and 0, 2 g of ammonium acetate in 18 g of water ,. Then, 15 g of ammonia (0.88 mol) and 20.5 g (0,) 6 of an aqueous solution of hydrogen peroxide are introduced. The autoclave is closed and heated for 2 hours at 70 ° C. under a pressure of 3 bar. At the end of the reaction, acetonazine is quantitatively analyzed. 30.7 g (0.27 mol) are obtained, which corresponds to 70% relative to the hydrogen peroxide used. Example 29. A solution of 42.5 g of f-methoxypropionitrile (0.5 mol), 58 g of acetone (1 mol), 18 g of water, 1 g of disodium salt of ethylenediaminetetraacetic acid and 0.1 g of acetic acid in 1 GO of methanol are introduced into the reactor. . Heat to 50 ° C and dissolve 15.3 g of ammonia (0.93 mol), inject it by bubbling ammonia gas. Then, 20.1 g (O, mol) of 70% aqueous hydrogen peroxide solution are added. The reaction is continued for 7 hours; it is introduced by sparging 1.6 g / h of ammonia gas. At the end of the reaction, it is established by conventional methods of quantitative analysis that the mixture contains 36 g of acetonazine (0.32 mol). This corresponds to a yield of 80%, relative to the hydrogen peroxide used. PRI-m er 30. Analogously to example 29, using instead of | 3-methoxypropionitrile g n-butyarnitrile (0.5 mol), receive a mixture containing 23.5 g of acetonazine (0.21 mol). 53% yield with respect to hydrogen peroxide used. Example 31. Analogously to Example 29, using .2.3 g. Of cyanacetic acid (0.5 mol) instead of -methoxypropionic and Trile, a mixture containing 11.7 g of acetone azine (0.105 mol) is obtained after 3 h of reaction. 26% yield relative to hydrogen peroxide used. Example 32. Analogously to example 29, using instead of / -methoxypropionitrile 100 g of cyan-9-oxa-7-nonanoic acid (0.5 mol), after 3 h of reaction, a mixture is obtained. 1 g of acetonazine. (0.125 mol). Yield 31% relative to the used hydrogen peroxide. Example 33. Analogously to example 29, replacing f-methoxypropionium and tril 35 g (-aminopionitrile (0.5 mol) to obtain a mixture containing 9, g of acetonazine (O, O mol). Output 21 relative to the used hydrogen peroxide. Example 3. Similarly, 29, replacements of / -metoxy-propionyl 2k g of imidiacetonitrile (0.25 mol, i.e. 0.5 equiv. of nitrile), after 5 h of reaction, a mixture containing 27 g of acetonazine (0.2A mol) is obtained. The yield is 6Q% relative used hydrogen peroxide. Example 35 Analogously to example 29, Using g (α-hydroxypropionitrile instead of |% -methoxypropionitrile (0.5 mol), a mixture containing 33 g of acetonazine (0.295 mol) is obtained, which corresponds to the% relative to hydrogen peroxide. Example Bt. Similarly to Example 29, using instead of p-methoxypropionitrile 33.5 g of methacrylonitrile (0.5 mol), a mixture containing 28 g of acetonazine (0.25 mol) is obtained, which corresponds to a yield of 62.5 relative to hydrogen peroxide Example 37 Analogously to Example 29, using 52 g of nicotinenitrile (0.5 mol) instead of p-methoxypropionitrile. get a mixture containing 30 g of acetonazine (0.27 mol), which corresponds to the output b7 relative to hydrogen peroxide. EXAMPLE 38 Analogously to example 29 using instead of b-methoxypropionitrile kS g (b-chloropropionitrile (0.5 mol), a mixture is obtained containing 29.5 acetonazine (o, 26 mol) which corresponds to a B5% yield relative to hydrogen peroxide. Example 39. 12.5 g of amber nitrile (0.125 mol, or 0.31 eq. of nitrile), 35 g of acetone (0.62 mol), 11.25 g of water, 0, B25 g of disodium salt are placed in the reactor. ethylenediaminetetraacetic acid and 0.1 g of ammonium acetate in 100 g of methanol. Heat to 0 ° C and dissolve (10.6 g of ammonia (0.625 mol) by bubbling), then 12.15 g (0.25 mol) of 70 % n of an aqueous solution of hydrogen peroxide. The mixture was incubated for 3 hours with light ammonia sparging. The mixture contains 18 g of acetonazine (0.16 mol), which corresponds to a yield of 6k% relative to hydrogen peroxide. Example tO. Analogously to example 39, using instead of amber nitrile 1, b5 g of glutarnitrile (0.155 mol), after 6 h of reaction (including the addition of additives, X 15.7 g of acetonazine (Q, k mol) are obtained, which corresponds to a yield of 5b% relative to hydrogen peroxide. Example Analogously to Example 39, using instead of amber nitrile 16.7 g of adiponitrile (0.155 mol), 1.5 g of acetonazine (0.13 mol) are obtained after 7 hours of the total reaction time, which corresponds to a yield of 52% relative to hydrogen peroxide. Analogously to example 37, using 19.2 g | 3-oxide-propionitrile (0.155 mol), to obtain 16.2 g of acetonazine (O, mol), corresponding to a yield of 58% relative to hydrogen peroxide. Example 3. In a reactor, put g of ethylenediaminetetraketonitrile (0.09 mol, or 0.36 eq. nitrile), 2 g of acetone ( 0.71 mol), 117 g of methanol, 13.2 water and 0.15 g of ammonium acetate. The mixture is heated to 50 ° C and 13.6 g of ammonia (0.8 mol) are dissolved by bubbling. The mixture is kept for 3 hours at the time of continuing. ammonia in the amount of 3 g / hour. The mixture contains 16 g of acetonazine (0.143 mol), which corresponds to a yield of 48% relative to hydrogen peroxide. Claims 1. A method for producing azines of the formula 1: V. , V "g where one of R and R is hydrogen, the other or both R and unbranched or branched lower alkyl or phenyl, or R and R together cycloalkyl with 6-12 carbon atoms based on ammonia and carbonyl compound of the formula P; (11) where RJ and Rj. have the indicated meanings. .1395962 characterized in that, in order to simplify the process, ammonia is reacted with a carbonyl compound and hydrogen peroxide in the presence of a nitrile of the formula JII K3- (; (m) 1-6; i is unsubstituted or substituted by halogen, hydroxyl groups, amino groups or carboxyl alkyl groups with 1-12 carbon atoms, is cycloalkyl, phenyl or a lower alkyl-substituted pyridine ring, with,
    [2]
    2. The method according to claim 1, characterized by the fact that the process is carried out in a different manner as acetic acid or acetic acid, ammonium.
    [3]
    3. The method according to paragraphs. 1-2, which is carried out in the presence of methanol as a solution. Priority signs: 12.06.70. Carrying out the process in the presence of a nitrile of the formula ZP and using a ketone of the formula I, December 29, 1970. Carrying out the process in the presence of a catalyst. 2t.02,71. Carrying out the process in the presence of a nitrile of the formula Sch 03.03.71. Using an aldehyde of the formula 3I. Sources of information, ntye taken into account in the examination 1. USSR Patent No. 328573, C 07 C 109/02, 1968 (prototype).
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    同族专利:
    公开号 | 公开日
    NO136536B|1977-06-13|
    LU63320A1|1971-09-13|
    YU35239B|1980-10-31|
    DK132945C|1976-08-02|
    US3972876A|1976-08-03|
    CH551381A|1974-07-15|
    YU136471A|1980-04-30|
    NO136536C|1977-09-21|
    DE2127229B2|1978-10-26|
    BE766845A|1971-10-01|
    IT942433B|1973-03-20|
    DE2127229C3|1979-06-21|
    DE2127229A1|1972-01-27|
    RO60164A|1976-08-15|
    SE389105B|1976-10-25|
    JPS5133083B1|1976-09-17|
    CA979015A|1975-12-02|
    AT316496B|1974-07-10|
    NL7108038A|1971-12-14|
    HU162436B|1973-02-28|
    NL154207B|1977-08-15|
    GB1357811A|1974-06-26|
    DK132945B|1976-03-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2870206A|1956-12-01|1959-01-20|Rhone Poulenc Sa|Preparation of benzophenone-azine|GB2021560B|1978-04-13|1982-09-08|Showa Denko Kk|Process for producing ketazines|
    EP0487160B2|1990-11-23|2001-11-07|Atofina|Process for the preparation of azines|
    WO2018065997A1|2016-10-03|2018-04-12|Council Of Scientific & Industrial Research|An improved process for production of hydrazine hydrate|
    FR3096048B1|2019-05-16|2021-04-30|Arkema France|IMPROVED PROCESS FOR THE PREPARATION OF HYDRAZINE HYDRATE WITH OXIME RECYCLING|
    FR3096049B1|2019-05-16|2021-12-17|Arkema France|IMPROVED PROCESS FOR THE PREPARATION OF HYDRAZINE HYDRATE WITH PYRAZOLINE RECYCLING|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR707021704A|FR2092734B1|1970-06-12|1970-06-12|
    FR7046994A|FR2122279B2|1970-12-29|1970-12-29|
    FR7106215A|FR2128021B2|1970-06-12|1971-02-24|
    FR7107249A|FR2127288A5|1971-03-03|1971-03-03|Preparation of azines|
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