LU84129A1 - PROCESS FOR THE METAL HALOGENATION OF N- (O, O'-DIALKYL PHENYL) ALANINATES AND APPROVALS - Google Patents
PROCESS FOR THE METAL HALOGENATION OF N- (O, O'-DIALKYL PHENYL) ALANINATES AND APPROVALS Download PDFInfo
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- LU84129A1 LU84129A1 LU84129A LU84129A LU84129A1 LU 84129 A1 LU84129 A1 LU 84129A1 LU 84129 A LU84129 A LU 84129A LU 84129 A LU84129 A LU 84129A LU 84129 A1 LU84129 A1 LU 84129A1
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- LU
- Luxembourg
- Prior art keywords
- formula
- alaninates
- approvals
- lewis acid
- dialkyl phenyl
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 19
- 230000026030 halogenation Effects 0.000 title description 3
- 238000005658 halogenation reaction Methods 0.000 title description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000002841 Lewis acid Substances 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- SNGROCQMAKYWRE-UHFFFAOYSA-N 2'-chlorobiphenyl-2,3-diol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)Cl)=C1O SNGROCQMAKYWRE-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 description 11
- -1 alkane carboxylic esters Chemical class 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- QNAYBMKLOCPYGJ-UHFFFAOYSA-M alaninate Chemical compound CC(N)C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-M 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- DWKPPFQULDPWHX-VKHMYHEASA-N l-alanyl ester Chemical compound COC(=O)[C@H](C)N DWKPPFQULDPWHX-VKHMYHEASA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
La présente invention concerne un nouveau procédé de préparation de N-(métahalogénophényl)-alaninates et produits homologues.The present invention relates to a new process for the preparation of N- (metahalogenophenyl) -alaninates and homologous products.
Les N-(métahalogénophényl)-alaninates et leurs ho-5 mologues sont des produits intermédiaires utiles dans la fabrication de nombreux pesticides, en particulier ceux décrits dans les brevets français 2267042 et européen 14167.N- (metahalophenyl) -alaninates and their ho-5 mologues are useful intermediates in the manufacture of many pesticides, in particular those described in French patents 2267042 and European patents 14167.
Il s'agit de produits de formule 10 R2· R1 R3 Xÿ) NH-kH - C00 - R4 · (I) R5 1 5 15 dans laquelle R et R représentent un groupe alkyleThese are products of formula 10 R2 · R1 R3 Xÿ) NH-kH - C00 - R4 · (I) R5 1 5 15 in which R and R represent an alkyl group
OO
(de préférence de l· à 4 atomes de carbone), R représente un atome d'halogène, notamment le brome et le chlore mais de préférence le chlore,.R3 représente l'atome d'hydrogène ou un radical méthyle, R4 représente un groupe al-'20 kyle (de préférence de 1 à 4 atomes de carbone).(preferably from 1 to 4 carbon atoms), R represents a halogen atom, in particular bromine and chlorine but preferably chlorine,. R3 represents the hydrogen atom or a methyl radical, R4 represents a al-'20 kyle group (preferably from 1 to 4 carbon atoms).
’ Jusqu’à présent on savait préparer les esters ana-lino alcane carboxyliques à partir d'anilines préalablement substituées (J.Org. Chem 30 p.4101 (1965); Tetrahedron 1967 x p.487-498 . Dans le cas de la préparation de composés de \ » 25 formule (I) et, plus généralement de N-(o,o'-dialkyl m-ha-logénophényl) alaninates, cela suppose qu'on utilise comme réactif de départ des ο,ο'-dialkyl m-halogéno anilines.'Up to now, it has been known to prepare the ana-lino alkane carboxylic esters from previously substituted anilines (J. Org. Chem 30 p. 4101 (1965); Tetrahedron 1967 x p. 487-498. preparation of compounds of formula (I) and, more generally of N- (o, o'-dialkyl m-ha-logenophenyl) alaninates, this presupposes that ο, ο'-dialkyl are used as starting reagent m-halo anilines.
Un but de 1'invention est d'éviter la nécessité de mettre en oeuvre de tels réactifs.An object of the invention is to avoid the need to use such reagents.
30 Un but de l'invention, dérivé du premier, est donc de fournir un procédé commode d'halogénation en méta de dérivés d'aniline ο,ο'-dialkylés et N-substitués.An object of the invention, derived from the first, is therefore to provide a convenient process for the meta halogenation of ο, ο'-dialkylated and N-substituted aniline derivatives.
Ori a déjà décrit 1'halogénation en méta de dérivés d'aniline ο,ο'-dialkylés et N-substitués (Synthesis, 1971 35 p.467).*Ce procédé, qui donne de bons rendements, est -V'.Ori has already described the meta halogenation of ο, ο'-dialkylated and N-substituted aniline derivatives (Synthesis, 1971 35 p.467). This process, which gives good yields, is -V '.
2 1 , r caractérisé par le fait qu'on opère en présence d'acide acétique mais ce procédé n'est pas satisfaisant dans le cas de la métahalogénation de produits de formule 5 /—< r1 f · /yS- NH - CH - COOR4 . (IX) '““C R5 dans laquelle R·*·, R3, R3, R4 ont les mêmes signi-10 fications que celles données ci-avant.2 1, r characterized in that it operates in the presence of acetic acid but this process is not satisfactory in the case of metahalogenation of products of formula 5 / - <r1 f · / yS- NH - CH - COOR4. (IX) '““ C R5 in which R · * ·, R3, R3, R4 have the same meanings as those given above.
Un but de l'invention est donc de fournir un pro-' 1 cédé convenable de métahalogénation des produits de formule (II).An object of the invention is therefore to provide a suitable process for metahalogenation of the products of formula (II).
Il a maintenant été trouvé, et c’est ce qui fait 15 l'objet de la présente invention, que ces buts pouvaient être atteints grâce à un procédé caractérisé, en ce qu'on fait réagir un halogène avec le composé de formule 20 'Cv)- NH - CH - COOR4 (II) ^-<R3 * dans laquelle R1, R3, R3 et R4 ont les signifi-. cations données ci-avant, en présence d'au moins 2 moles 25 d'acide de Lewis par.mole de composé de formule (II).It has now been found, and this is the object of the present invention, that these objects can be achieved by a characterized process, in that a halogen is reacted with the compound of formula 20 ' Cv) - NH - CH - COOR4 (II) ^ - <R3 * in which R1, R3, R3 and R4 have the meanings. cations given above, in the presence of at least 2 moles of Lewis acid per mole of compound of formula (II).
Le rapport molaire acide de Lewis/composé de formule (II) est généralement compris entre 2,5 et 4, de préférence entre 3 et 3,5.The Lewis acid / compound molar ratio of formula (II) is generally between 2.5 and 4, preferably between 3 and 3.5.
Comme halogène, on utilise en pratique un halogène 30. à l'état moléculaire, de préférence le chlore ou le brome.As halogen, in practice a halogen 30 is used in the molecular state, preferably chlorine or bromine.
Comme acides de Lewis utilisables on peut citer Al Cl3, AlBr3, BF3>.SnCl4, TiCl^.As Lewis acids which can be used, mention may be made of Al Cl3, AlBr3, BF3> .SnCl4, TiCl 4.
Le procédé de l'invention s'applique particulièrement bien au composé tel que Rl= r5 = r3 - r4 - ch^ et 35 r2 = r.l.‘The process of the invention applies particularly well to the compound such that Rl = r5 = r3 - r4 - ch ^ and 35 r2 = r.l. ‘
La réaction est généralement effectuée en présence 3 * b 4 k d'un solvant inerte, c'est à dire ne réagissant pas chimiquement avec les réactifs ou produits de réaction dans les conditions opératoires.The reaction is generally carried out in the presence of 3 * b 4 k of an inert solvent, that is to say that does not react chemically with the reagents or reaction products under the operating conditions.
Comme solvants appropriés on peut citer les hydro-5 carbures aliphatiques polyhalogénés liquides à la température mise en oeuvre, notamment le dichloro-1,2 éthane et le tétrachlorure de carbone.As suitable solvents, mention may be made of polyhalogenated aliphatic hydro-5 carbides which are liquid at the temperature used, in particular 1,2-dichloroethane and carbon tetrachloride.
La température du mélange réactionnel est généralement comprise entre -10°C et le point d'ébullition du sol-10 vant, de préférence entre 15 et 40°C. Il est particulièrement commode d'opérer à température ambiante.The temperature of the reaction mixture is generally between -10 ° C and the boiling point of the soil-10 before, preferably between 15 and 40 ° C. It is particularly convenient to operate at room temperature.
J La concentration en composés' de formule (I) et (II) est généralement comprise, en tout, entre 0,2 et 5 mole/1 de préférence entre 0,5 et 3 mole/1.The concentration of compounds' of formula (I) and (II) is generally, in all, between 0.2 and 5 mole / 1, preferably between 0.5 and 3 mole / 1.
15 II doit bien.être entendu que le présent exposé n’indique pas la nature des mécanismes réactionnels et se borne à décrire les moyens mis en oeuvre ; en particulier le procédé de l'invention se caractérise par une réaction à l'aide de 3 produits (réactifs) : le produit de formule 20 (II), l'halogène et l'acide de Lewis, étant bien entendu qu'il peut intervenir des réactions préalables de nature plus ou mo.ins déterminée. Ainsi l'acide de Lewis peut s'additionner sur le composé de formule (II) avant même que Γ - ·. l'halogène réagisse ; il est clair que ce déroulement par- 25 ticulier des opérations ou phénomènes réactionnels entre dans le cadre général qui a été décrit pour le procédé de l'invention.15 It should be understood that this presentation does not indicate the nature of the reaction mechanisms and is limited to describing the means used; in particular the process of the invention is characterized by a reaction using 3 products (reactants): the product of formula 20 (II), halogen and Lewis acid, it being understood that it can intervene preliminary reactions of more or less determined nature. Thus Lewis acid can add up on the compound of formula (II) even before Γ - ·. halogen reacts; it is clear that this particular course of reaction operations or phenomena falls within the general framework which has been described for the process of the invention.
Les exemples suivants, donnés à titre non limitatif, illustrent l'invention et montrent comment elle peut 30- être mise 'en oeuvre.The following examples, given without limitation, illustrate the invention and show how it can be implemented.
EXEMPLE 1 A une suspension de 801 g de AlCl^ dans 1,6 1 de dichloro-1,2 éthane, on ajoute, goutte à goutte et en agitant le milieu réactionnel, 414 g de N-(diméthyl-2,6 phé-35 nyl) alanir.ate de méthyle. On refroidit à l'aide d'un bain d'eau glacée de manière à maintenir le milieu réactionnel à < · • 5 i 4 20°C. Après la fin de l'addition, on poursuit l'agitation en maintenant la température à 20°C. On injecte alors dans le milieu 142 g de chlore gazeux à raison de 2g/mn. Le milieu réactionnel est refroidi de manière à être maintenu à 5 25°C. Après fin de l'addition on poursuit l'agitation pen dant 1/2 heure puis on hydrolyse en versant lentement le mélange réactionnel sur 3 kg de glace pilée sous agitation. On décante, sépare la phase organique, lave celle-ci deux fois avec 0,3 1 d'acide chlorhydrique aqueux N chaque fois, 10 puis deux fois avec 0,3 1 d'eau chaque fois.EXAMPLE 1 To a suspension of 801 g of AlCl 4 in 1.6 l of 1,2-dichloroethane, 414 g of N- (2,6-dimethyl phephide) are added dropwise with stirring the reaction medium. 35 nyl) methyl alanir.ate. Cooled using an ice water bath so as to maintain the reaction medium at <· • 5 i 4 20 ° C. After the end of the addition, stirring is continued while maintaining the temperature at 20 ° C. 142 g of chlorine gas are then injected into the medium at a rate of 2 g / min. The reaction medium is cooled so as to be kept at 25 ° C. After the end of the addition, stirring is continued for 1/2 hour, then hydrolysis is carried out by slowly pouring the reaction mixture onto 3 kg of crushed ice with stirring. Decanted, the organic phase is separated, the latter is washed twice with 0.3 l of aqueous hydrochloric acid N each time, then twice with 0.3 l of water each time.
. Cette phase organique lavée est évaporée de manière à éliminer le solvant. On obtient 417 g (rendement : 86 35) d'une huile constituée du produit de formule. This washed organic phase is evaporated so as to remove the solvent. 417 g are obtained (yield: 86 35) of an oil consisting of the product of formula
Cl ^CH? ÇH3 15 (7)_ NH - CH - COOCH, \-<ch3Cl ^ CH? ÇH3 15 (7) _ NH - CH - COOCH, \ - <ch3
Le produit peut être purifié par distillation à 1Ô0°C sous pression absolue de 0,5 mm de mercure ( = 0,66 20 millibar). Le produit ainsi purifié est un produit cristal lin fondant à 43,5°C.The product can be purified by distillation at 10 ° C under absolute pressure of 0.5 mm of mercury (= 0.66 millibar). The product thus purified is a flax crystal product melting at 43.5 ° C.
L'Obtention de pesticides à partir de produits de formule (I) peut être réalisée par tout moyen connu en par- (J) ·. ticulier par réaction de chlorures d'acides porteurs des 25 groupes fonctionnels·adéquats. Ces techniques sont décrites • en particulier dans les brevets français 2267042 et euro péen 14167.Obtaining pesticides from products of formula (I) can be carried out by any means known in par- (J) ·. especially by reaction of acid chlorides carrying the 25 appropriate functional groups. These techniques are described • in particular in French patents 2267042 and European patents 14167.
EXEMPLE 2EXAMPLE 2
On reproduit l'exemple 1, en remplaçant l'alaninate 30. de départ'par une même quantité molaire de N-(diéthyl-2,6 phényl) alaninate de méthyle.Example 1 is reproduced, replacing the starting alaninate 30 with the same molar amount of methyl N- (2,6-diethylphenyl) alaninate.
On obtient le N-(chloro-3 diéthyl-2,6 phényl) alaninate de méthyle avec un rendement de 64 35. Son indice de réfraction à 20°C pour la raie 0 du sodium (n 20) est 35 égal à 1,528. Son point d'ébullition sous une pression ao-solue de 0,4 mm de mercure (=0,53 millibar) est de 115°C.Methyl N- (3-chloro-2,6-phenylphenyl) alaninate is obtained with a yield of 64 35. Its refractive index at 20 ° C. for the sodium line 0 (n 20) is equal to 1.528. Its boiling point under an ao-solute pressure of 0.4 mm of mercury (= 0.53 millibar) is 115 ° C.
• \ 5 EXEMPLE 3• \ 5 EXAMPLE 3
On reproduit l'exemple 1, mais en remplaçant l'ala-. ninate par une même quantité molaire de N-(diisopropyl-2,6 phényl) alaninate de méthyle. On obtient le N-(chloro-3 5 dlisopropyl-2,6 phényl) alaninate de méthyle avec un rendement de 33 % sous forme d'une huile d'indice de réfraction (n20 égal à 1,521). Son point d'ébullition, sous une pression absolue de 1 mmHg (=1,3 millibar) est de 130-135°C.Example 1 is reproduced, but replacing ala-. ninate with the same molar amount of methyl N- (2,6-diisopropylphenyl) alaninate. N- (3-chloro-2,6-isopropylphenyl) methyl alaninate is obtained with a yield of 33% in the form of an oil with a refractive index (n20 equal to 1.521). Its boiling point, under an absolute pressure of 1 mmHg (= 1.3 millibar) is 130-135 ° C.
) ”· .) ”·.
m • *, » Ψ i \ · '·. ' \ \ · . , a i 9 *m • *, ”Ψ i \ · '·. '\ \ ·. , a i 9 *
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8109379 | 1981-05-08 | ||
| FR8109379A FR2505327A1 (en) | 1981-05-08 | 1981-05-08 | PROCESS FOR THE METAL HALOGENATION OF N- (O, O'-DIALKYL PHENYL) ALANINATES AND APPROVALS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| LU84129A1 true LU84129A1 (en) | 1984-03-07 |
Family
ID=9258312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| LU84129A LU84129A1 (en) | 1981-05-08 | 1982-05-05 | PROCESS FOR THE METAL HALOGENATION OF N- (O, O'-DIALKYL PHENYL) ALANINATES AND APPROVALS |
Country Status (7)
| Country | Link |
|---|---|
| BE (1) | BE893117A (en) |
| DE (1) | DE3217029A1 (en) |
| FR (1) | FR2505327A1 (en) |
| GB (1) | GB2098210A (en) |
| IT (1) | IT1152114B (en) |
| LU (1) | LU84129A1 (en) |
| NL (1) | NL8201764A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01106850A (en) * | 1986-09-02 | 1989-04-24 | Ciba Geigy Ag | Manufacture of n-acyl-n-alkyl-2,6-dialkyl-3- chloroaniline |
| EP0310732B1 (en) * | 1987-10-09 | 1992-03-11 | Ciba-Geigy Ag | Process for the preparation of n-acyl-n-alkyl-2,6-dialkyl-3-chloroanilines |
| US4721797A (en) * | 1986-09-02 | 1988-01-26 | Ciba-Geigy Corporation | Process for the preparation of N-acyl-N-alkyl-2,6-dialkyl-3-chloroanilines |
| US4918230A (en) * | 1988-06-14 | 1990-04-17 | Ciba-Geigy Corporation | Process for the preparation 4-bromoaniline hydrobromides |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1730729A (en) * | 1926-10-06 | 1929-10-08 | Gen Aniline Works Inc | Chlorsubstituted product of the 1-amino-2.4-dimethylbenzene and process of preparing it |
| US2813118A (en) * | 1953-07-16 | 1957-11-12 | American Cystoscope Makers Inc | X-ray contrast compounds |
| OA04979A (en) * | 1974-04-09 | 1980-11-30 | Ciba Geigy | New aniline derivatives useful as microbicidal agents and their preparation process. |
-
1981
- 1981-05-08 FR FR8109379A patent/FR2505327A1/en active Granted
-
1982
- 1982-04-28 NL NL8201764A patent/NL8201764A/en not_active Application Discontinuation
- 1982-05-04 IT IT21070/82A patent/IT1152114B/en active
- 1982-05-05 GB GB8213005A patent/GB2098210A/en not_active Withdrawn
- 1982-05-05 LU LU84129A patent/LU84129A1/en unknown
- 1982-05-06 DE DE19823217029 patent/DE3217029A1/en not_active Withdrawn
- 1982-05-07 BE BE0/208038A patent/BE893117A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BE893117A (en) | 1982-11-08 |
| IT8221070A0 (en) | 1982-05-04 |
| DE3217029A1 (en) | 1982-11-25 |
| FR2505327B1 (en) | 1984-08-10 |
| GB2098210A (en) | 1982-11-17 |
| IT1152114B (en) | 1986-12-31 |
| FR2505327A1 (en) | 1982-11-12 |
| NL8201764A (en) | 1982-12-01 |
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