EP1268394A1 - Method for preparing alkyl nitrites - Google Patents

Method for preparing alkyl nitrites

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Publication number
EP1268394A1
EP1268394A1 EP01921463A EP01921463A EP1268394A1 EP 1268394 A1 EP1268394 A1 EP 1268394A1 EP 01921463 A EP01921463 A EP 01921463A EP 01921463 A EP01921463 A EP 01921463A EP 1268394 A1 EP1268394 A1 EP 1268394A1
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Prior art keywords
nitrite
acid
alkyl
reaction
general formula
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EP01921463A
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German (de)
French (fr)
Inventor
Philippe Karrer
Sébastien BALZANO
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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Publication of EP1268394A1 publication Critical patent/EP1268394A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/04—Preparation of esters of nitrous acid

Definitions

  • the invention relates to the synthesis of alkyl nitrites continuously by reaction of an alcohol with a mineral nitrite in an acid medium.
  • the alkyl nitrites are used, inter alia, in the field of pharmacy as vasodilators, in the field of dyes as nitrosating reagents, in the field of polymers as reaction catalysts or even as additives for fuels.
  • the alkyl nitrites can be obtained by several routes.
  • a first route described by Matsunaga et al. [Kogyo Kayaku (1980), 41 (1), 3-7] consists in reacting an alkyl halide on a mineral nitrite, in particular sodium nitrite.
  • a second way consists in reacting an aliphatic alcohol with a nitrosating reagent.
  • the nitrosating reagent can be nitrosyl chloride, as described by Hiroshi et al. [J. Chem. Soc. Perkin Trans I; (1992), 14, 1837-1842].
  • the nitrosating reagent can also be nitrous acid, which is generated in situ by adding a mineral nitrite to the aliphatic alcohol in the presence of a strong acid.
  • the work of the inventors, authors of the present invention has resulted in a continuous process which makes it possible in a simple and economical way to prepare alkyl nitrites by reaction of nitrous acid, formed in situ, on an aliphatic alcohol, with high productivity. as a final product.
  • the subject of the present invention is a process for the preparation of alkyl nitrites of formula I:
  • R-ONO (I) in which R represents a linear or branched C 1 -C 20 alkyl group, advantageously C 2 -C ⁇ o, characterized in that one adds progressively and continuously in an aqueous medium
  • nitrite of formula III M NO 2 (III) in which M represents an alkali or alkaline earth metal cation, and
  • R represents a C2-C5 alkyl group.
  • M preferably represents sodium or potassium.
  • the mineral acid is advantageously a strong acid.
  • strong acid is meant an acid having a pKa of less than 3.3.
  • hydrochloric acid As strong acid, mention may be made of hydrochloric acid or sulfuric acid.
  • the concentration of the strong acid solution supplied to the reaction medium is at least 35%.
  • the reaction is carried out at a temperature between 0 ° C and 15 ° C, advantageously between 0 ° C and 5 ° C.
  • the reagents are added simultaneously and continuously so that the reactive species are present in the reaction medium at low instantaneous concentrations.
  • the concentrations of the reactive species in the aqueous reaction medium do not exceed 6, 1-6.2, 4-5 and 6.3-7.5 ⁇ mol / l for the aliphatic alcohol, the mineral nitrite and strong acid respectively.
  • the molar ratio of the strong acid to the alcohol is from 1 to 1.5, and preferably from 1 to 1.1, and the molar ratio of the strong acid to the nitrite is not greater than 1.
  • a base stock is prepared comprising an aqueous medium, a fraction of the compound of general formula II and a fraction of the compound of general formula III, b) is gradually added and continuously at this stock level said strong acid, the remaining amount of said alcohol of general formula II and the remaining amount of metallic nitrite of general formula III. It is also possible to use correctly calibrated metering pumps, which allows step a) to be omitted.
  • the product of general formula I formed is continuously withdrawn from the reaction medium and a continuous drying of the product formed is carried out. This can be carried out on a column of molecular sieve or potash.
  • the drying of the final product further increases the stability of the product formed over time by eliminating the water and the traces of acidity prescribed in the nitrous ester and responsible for the decomposition of the product.
  • the foot of water containing the salt is cooled to 2 ⁇ 2 ° C. and the 3 reagents are added simultaneously to this temperature in approximately 1 hour (very exothermic reaction). It is maintained for 5 minutes at this temperature.
  • the organic phase is dried by passage over a column of potash.
  • the foot of water containing the salt is cooled to 2 ⁇ 2 ° C and the 3 reagents are added simultaneously to this temperature in about 1 hour (exothermic reaction, cooling in brine at -12 ° C).
  • the upper organic phase is washed with:
  • the organic phase (226 g) is then dried by passage over a molecular sieve.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention concerns a method for preparing alkyl nitrites of formula (I) R ONO wherein R represents a C1-C20, advantageously C2-C10 linear or branched alkyl group. The invention is characterised in that it consists in gradually and continuously adding in an aqueous medium, an alcohol of formula (II) R OH, R being as defined above, a nitrite of formula (III) M NO2, wherein M represents a metal cation, and a strong acid, so as to form continuously said alkyl nitrite, and in continuously drawing off said alkyl nitrite thus formed from the reaction medium.

Description

PROCEDE DE PREPARATION DE NITRITES D'ALKYLES. PROCESS FOR THE PREPARATION OF ALKYL NITRITES.
L'invention concerne la synthèse de nitrites d'alkyles en continu par réaction d'un alcool avec un nitrite minéral en milieu acide.The invention relates to the synthesis of alkyl nitrites continuously by reaction of an alcohol with a mineral nitrite in an acid medium.
Les nitrites d'alkyles sont utilisés, entre autres, dans le domaine de la pharmacie comme vasodilatateurs, dans le domaine des colorants comme réactifs nitrosants, dans le domaine des polymères comme catalyseurs de réaction ou encore comme additifs pour les carburants. Les nitrites d'alkyles peuvent être obtenus par plusieurs voies. Une première voie décrite par Matsunaga et al. [Kogyo Kayaku (1980), 41(1), 3-7] consiste à faire réagir un halogénure d'alkyle sur un nitrite minéral, notamment le nitrite de sodium.The alkyl nitrites are used, inter alia, in the field of pharmacy as vasodilators, in the field of dyes as nitrosating reagents, in the field of polymers as reaction catalysts or even as additives for fuels. The alkyl nitrites can be obtained by several routes. A first route described by Matsunaga et al. [Kogyo Kayaku (1980), 41 (1), 3-7] consists in reacting an alkyl halide on a mineral nitrite, in particular sodium nitrite.
Une seconde voie consiste à faire réagir un alcool aliphatique avec un réactif nitrosant.A second way consists in reacting an aliphatic alcohol with a nitrosating reagent.
Le réactif nitrosant peut être le chlorure de nitrosyle, comme décrit par Hiroshi et al. [J. Chem. Soc. Perkin Trans I ; (1992), 14, 1837-1842].The nitrosating reagent can be nitrosyl chloride, as described by Hiroshi et al. [J. Chem. Soc. Perkin Trans I; (1992), 14, 1837-1842].
Le réactif nitrosant peut également être l'acide nitreux, lequel est généré in situ par addition à l'alcool aliphatique d'un nitrite minéral en présence d'un acide fort.The nitrosating reagent can also be nitrous acid, which is generated in situ by adding a mineral nitrite to the aliphatic alcohol in the presence of a strong acid.
Cette voie de synthèse est décrite notamment par Hiroshi et al. (précité), T.J. Blacklock [J. Org. Chem. (1989) ; 54(16), 3907-3913] et S. Glover [S. Afr. J. Chem. ; (1981) 34(4), 96-100].This synthetic route is described in particular by Hiroshi et al. (cited above), T.J. Blacklock [J. Org. Chem. (1989); 54 (16), 3907-3913] and S. Glover [S. Afr. J. Chem. ; (1981) 34 (4), 96-100].
Tous les procédés de synthèse de nitrites d'alkyle à partir d'un alcool aliphatique et d'un nitrite minéral mis en œuvre à ce jour reposent sur des opérations en batch avec comme principaux inconvénients une faible productivité et un risque accru de dégradation du produit lié à son temps de séjour important dans le milieu réactionnel.All the processes for the synthesis of alkyl nitrites from an aliphatic alcohol and a mineral nitrite implemented to date are based on batch operations with the main disadvantages of low productivity and an increased risk of product degradation. linked to its long residence time in the reaction medium.
Les travaux des inventeurs auteurs de la présente invention ont abouti à un procédé en continu qui permet de façon simple et économique de préparer des nitrites d'alkyles par réaction d'acide nitreux, formé in situ, sur un alcool aliphatique, avec une productivité élevée en produit final. La présente invention a pour objet un procédé de préparation de nitrites d'alkyles de formule I :The work of the inventors, authors of the present invention, has resulted in a continuous process which makes it possible in a simple and economical way to prepare alkyl nitrites by reaction of nitrous acid, formed in situ, on an aliphatic alcohol, with high productivity. as a final product. The subject of the present invention is a process for the preparation of alkyl nitrites of formula I:
R-ONO (I) dans laquelle R représente un groupement alkyle linéaire ou ramifié en C1-C20, avantageusement en C2-Cιo, caractérisé en ce que l'on ajoute de manière progressive et continue dans un milieu aqueuxR-ONO (I) in which R represents a linear or branched C 1 -C 20 alkyl group, advantageously C 2 -Cιo, characterized in that one adds progressively and continuously in an aqueous medium
- un alcool de formule II : R OH (11) R étant tel que défini ci-dessus,an alcohol of formula II: R OH (11) R being as defined above,
- un nitrite de formule III : M NO2 (III) dans laquelle M représente un cation métallique alcalin, ou alcalino-terreux, eta nitrite of formula III: M NO 2 (III) in which M represents an alkali or alkaline earth metal cation, and
- un acide fort, de manière à former de manière continue ledit nitrite d'alkyle, et en ce que l'on soutire de manière continue ledit nitrite d'alkyle ainsi formé du milieu réactionnel. Avantageusement, R représente un groupement alkyle en C2-C5.- a strong acid, so as to continuously form said alkyl nitrite, and in that said alkyl nitrite thus formed is continuously drawn off from the reaction medium. Advantageously, R represents a C2-C5 alkyl group.
M représente de préférence le sodium ou le potassium. L'acide minéral est avantageusement un acide fort. Par acide fort, on entend un acide ayant un pKa inférieur à 3,3.M preferably represents sodium or potassium. The mineral acid is advantageously a strong acid. By strong acid is meant an acid having a pKa of less than 3.3.
Comme acide fort, on peut citer l'acide chlorhydrique ou l'acide sulfurique.As strong acid, mention may be made of hydrochloric acid or sulfuric acid.
De manière préférée, la concentration de la solution d'acide fort apportée au milieu réactionnel est d'au moins 35%.Preferably, the concentration of the strong acid solution supplied to the reaction medium is at least 35%.
La réaction est effectuée à une température comprise entre 0°C et 15°C, avantageusement entre 0°C et 5°C. Les réactifs sont ajoutés simultanément et de manière continue de manière à ce que les espèces réactives soient présentes dans le milieu réactionnel à des concentrations instantanées faibles.The reaction is carried out at a temperature between 0 ° C and 15 ° C, advantageously between 0 ° C and 5 ° C. The reagents are added simultaneously and continuously so that the reactive species are present in the reaction medium at low instantaneous concentrations.
De préférence, on veille à ce que les concentrations des espèces réactives dans le milieu réactionnel aqueux ne dépassent pas 6, 1-6,2, 4-5 et 6,3-7,5 μmol/l pour l'alcool aliphatique, le nitrite minéral et l'acide fort respectivement. Avantageusement, le rapport molaire de l'acide fort à l'alcool est de 1 à 1 ,5, et préférentiellement de 1 à 1 ,1 , et le rapport molaire de l'acide fort au nitrite n'est pas supérieur à 1.Preferably, it is ensured that the concentrations of the reactive species in the aqueous reaction medium do not exceed 6, 1-6.2, 4-5 and 6.3-7.5 μmol / l for the aliphatic alcohol, the mineral nitrite and strong acid respectively. Advantageously, the molar ratio of the strong acid to the alcohol is from 1 to 1.5, and preferably from 1 to 1.1, and the molar ratio of the strong acid to the nitrite is not greater than 1.
Ces conditions doivent être satisfaites pendant le déroulement de la réaction.These conditions must be satisfied during the course of the reaction.
Toutefois, en début de réaction, les rapports molaires indiqués précédemment peuvent dépasser les limites indiquées.However, at the start of the reaction, the molar ratios indicated above may exceed the limits indicated.
Selon une première variante du mode de réalisation de l'invention : a) on prépare un pied de cuve comprenant un milieu aqueux, une fraction du composé de formule générale II et une fraction du composé de formule générale III, b) on ajoute progressivement et de manière continue à ce pied de cuve ledit acide fort, la quantité restante dudit alcool de formule générale II et la quantité restante du nitrite métallique de formule générale III. II est également possible d'utiliser des pompes doseuses correctement étalonnées, ce qui permet l'omission de l'étape a).According to a first variant of the embodiment of the invention: a) a base stock is prepared comprising an aqueous medium, a fraction of the compound of general formula II and a fraction of the compound of general formula III, b) is gradually added and continuously at this stock level said strong acid, the remaining amount of said alcohol of general formula II and the remaining amount of metallic nitrite of general formula III. It is also possible to use correctly calibrated metering pumps, which allows step a) to be omitted.
Selon une seconde variante du procédé de l'invention, on soutire de manière continue du milieu réactionnel le produit de formule générale I formé et on procède à un assèchement en continu du produit formé. Celui-ci peut être réalisé sur une colonne de tamis moléculaire ou de potasse.According to a second variant of the process of the invention, the product of general formula I formed is continuously withdrawn from the reaction medium and a continuous drying of the product formed is carried out. This can be carried out on a column of molecular sieve or potash.
De cette manière, le faible temps de séjour du produit formé en milieu acide réduit les risques de dégradation de l'ester nitreux.In this way, the short residence time of the product formed in an acid medium reduces the risks of degradation of the nitrous ester.
L'assèchement du produit final permet encore d'accroître la stabilité du produit formé au cours du temps en éliminant l'eau et les traces d'acidité prescrits dans l'ester nitreux et responsables de la décomposition du produit.The drying of the final product further increases the stability of the product formed over time by eliminating the water and the traces of acidity prescribed in the nitrous ester and responsible for the decomposition of the product.
Les exemples ci-après illustrent l'invention. EXEMPLESThe following examples illustrate the invention. EXAMPLES
EXEMPLE 1 :EXAMPLE 1:
Préparation de nitrite de n-butyle.Preparation of n-butyl nitrite.
Dans un réacteur cylindrique d'un litre, muni d'une agitation, d'un réfrigérant et de trois ampoules d'addition, on charge sous azote, en pied :In a cylindrical reactor of one liter, fitted with a stirrer, a condenser and three addition funnels, the following is charged under nitrogen:
• 92 g d'eau à 5% en chlorure de sodium technique.• 92 g of water at 5% technical sodium chloride.
Les trois ampoules d'addition sont chargées respectivement avec : • 185,3 g de n-butanolThe three addition ampoules are loaded respectively with: • 185.3 g of n-butanol
• 461 ,4 g de solution aqueuse à 40% de nitrite de sodium (1 ,07 éq)• 461.4 g of 40% aqueous sodium nitrite solution (1.07 eq)
• 273,8 g d'acide chlorhydrique à 35 % (1 ,05 éq).• 273.8 g of 35% hydrochloric acid (1.05 eq).
On ajoute préalablement 10%» du n-butanol et 10% de la solution aqueuse de NaNO2 au pied d'eau pour démarrer avec un léger excès de ces réactifs et ainsi éviter de perdre NaN02 sous forme d'acide nitreux.10% of the n-butanol and 10% of the aqueous NaNO 2 solution are added beforehand to the bottom of the water to start with a slight excess of these reagents and thus avoid losing NaNO 2 in the form of nitrous acid.
Les vapeurs nitreuses éventuelles sont piégées dans un ballon contenantAny nitrous vapors are trapped in a flask containing
400 g d'eau et 200 g de potasse à 50%.400 g of water and 200 g of 50% potash.
On refroidit le pied d'eau contenant le sel à 2 ± 2°C et l'on ajoute simultanément les 3 réactifs à cette température en environ 1 heure (réaction très exothermique). On maintient 5 minutes à cette température.The foot of water containing the salt is cooled to 2 ± 2 ° C. and the 3 reagents are added simultaneously to this temperature in approximately 1 hour (very exothermic reaction). It is maintained for 5 minutes at this temperature.
La phase aqueuse inférieure est siphonnée et la phase organique supérieure lavée avec :The lower aqueous phase is siphoned off and the upper organic phase washed with:
• 92,6 g d'eau.• 92.6 g of water.
La phase organique est séchée par passage sur une colonne de potasse.The organic phase is dried by passage over a column of potash.
On obtient ainsi 246,6 g de nitrite de n-butyle sec soit un rendement de 95,6% titrant 97-98% de pureté, (teneur CPV en n-butanol : 1 ,7-1 ,9%).246.6 g of dry n-butyl nitrite are thus obtained, ie a yield of 95.6% grading 97-98% of purity, (CPV content of n-butanol: 1.7-1.9%).
EXEMPLE 2 :EXAMPLE 2:
Préparation de nitrite d'isoamyle. Dans un réacteur cylindrique d'un litre, muni d'une agitation, d'un réfrigérant et de trois ampoules d'addition, on charge sous azote, en pied :Preparation of isoamyl nitrite. In a cylindrical reactor of one liter, fitted with a stirrer, a condenser and three addition funnels, the following is charged under nitrogen:
• 77 g d'eau à 5% en chlorure de sodium technique.• 77 g of water at 5% technical sodium chloride.
Les trois ampoules d'addition sont chargées respectivement avec : • 176,2 g (2 mol.) d'alcool isoamyliqueThe three addition ampoules are loaded respectively with: • 176.2 g (2 mol.) Of isoamyl alcohol
• 370 g de solution aqueuse à 40% de nitrite de sodium (1 ,07 éq)• 370 g of 40% aqueous sodium nitrite solution (1.07 eq)
• 219,3 g d'acide chlorhydrique à 35% (1,05 éq).• 219.3 g of 35% hydrochloric acid (1.05 eq).
On ajoute préalablement 10% de l'alcool isoamylique et 10% de la solution aqueuse de NaNO2 au pied d'eau pour démarrer avec un léger excès de ces réactifs et ainsi éviter de perdre NaN02 sous forme d'acide nitreux.10% of the isoamyl alcohol and 10% of the aqueous NaNO 2 solution are added beforehand to the bottom of the water to start with a slight excess of these reagents and thus avoid losing NaNO 2 in the form of nitrous acid.
Les vapeurs nitreuses éventuelles sont piégées dans un ballon contenant une solution de potasse.Any nitrous vapors are trapped in a flask containing a potassium solution.
On refroidit le pied d'eau contenant le sel à 2 ± 2°C et l'on ajoute simultanément les 3 réactifs à cette température en environ 1 heure (réaction exothermique, refroidissement à la saumure à -12°C).The foot of water containing the salt is cooled to 2 ± 2 ° C and the 3 reagents are added simultaneously to this temperature in about 1 hour (exothermic reaction, cooling in brine at -12 ° C).
La phase organique supérieure est lavée avec :The upper organic phase is washed with:
• 2 x 60 g d'eau.• 2 x 60 g of water.
La phase organique (226 g) est ensuite séchée par passage sur un tamis moléculaire.The organic phase (226 g) is then dried by passage over a molecular sieve.
On obtient ainsi 226 g de nitrite d'isoamyle sec, soit un rendement de 96,4% titrant 98% de pureté. 226 g of dry isoamyl nitrite are thus obtained, ie a yield of 96.4% titrating 98% of purity.

Claims

REVENDICATIONS
1. Procédé de préparation de nitrites d'alkyles de formule I :1. Process for the preparation of alkyl nitrites of formula I:
R-ONO (I) dans laquelle R représente un groupement alkyle linéaire ou ramifié en C1-C20. avantageusement C2-C10, caractérisé en ce que l'on ajoute de manière progressive et continue dans un milieu aqueuxR-ONO (I) in which R represents a linear or branched C1-C20 alkyl group. advantageously C2-C10, characterized in that a progressive and continuous addition is added to an aqueous medium
- un alcool de formule II- an alcohol of formula II
R OH (II) R étant tel que défini ci-dessus,R OH (II) R being as defined above,
- un nitrite de formule III- a nitrite of formula III
M N02 (III) dans laquelle M représente un cation métallique de préférence alcalin ou alcalino-terreux, et - un acide fort, de préférence minéral, de manière à former de manière continue ledit nitrite d'alkyle, et en ce que l'on soutire de manière continue ledit nitrite d'alkyle ainsi formé du milieu réactionnel.M NO 2 (III) in which M represents a metallic cation preferably alkaline or alkaline-earth, and - a strong acid, preferably mineral, so as to continuously form said alkyl nitrite, and in that the said alkyl nitrite thus formed is continuously withdrawn from the reaction medium.
2. Procédé selon la revendication 1 , caractérisé en ce que l'on assèche le nitrite d'alkyle soutiré du milieu réactionnel.2. Method according to claim 1, characterized in that the alkyl nitrite withdrawn from the reaction medium is dried.
3. Procédé selon la revendication 1 , caractérisé en ce qu'au cours de la réaction, la concentration en alcool de formule II n'est pas supérieure à 6,1-6,2 μmol/l.3. Method according to claim 1, characterized in that during the reaction, the alcohol concentration of formula II is not greater than 6.1-6.2 μmol / l.
4. Procédé selon la revendication 1 , caractérisé en ce qu'au cours de la réaction, la concentration en nitrite de formule III n'est pas supérieure à 4-5 μmol/l.4. Method according to claim 1, characterized in that during the reaction, the nitrite concentration of formula III is not greater than 4-5 μmol / l.
5. Procédé selon la revendication 1 , caractérisé en ce qu'au cours de la réaction, la concentration en acide minéral n'est pas supérieure à 6,3-7,5 μmol/l. 5. Method according to claim 1, characterized in that during the reaction, the concentration of mineral acid is not greater than 6.3-7.5 μmol / l.
6. Procédé selon la revendication 1 , caractérisé en ce que le rapport molaire de l'acide à l'alcool est de 1 à 1 ,5, de préférence 1 à 1 ,1.6. Method according to claim 1, characterized in that the molar ratio of acid to alcohol is 1 to 1.5, preferably 1 to 1.1.
7. Procédé selon la revendication 1 , caractérisé en ce que le rapport molaire de l'acide au nitrite n'est pas supérieur à 1.7. Method according to claim 1, characterized in that the molar ratio of acid to nitrite is not greater than 1.
8. Procédé selon la revendication 1 , caractérisé en ce que a) l'on prépare un pied de cuve comprenant un milieu aqueux, une fraction du composé de formule générale II et une fraction du composé de formule générale III, b) l'on ajoute progressivement et de manière continue à ce pied de cuve ledit acide, la quantité restante dudit alcool de formule générale II et la quantité restante du nitrite métallique de formule générale III.8. Method according to claim 1, characterized in that a) preparing a base stock comprising an aqueous medium, a fraction of the compound of general formula II and a fraction of the compound of general formula III, b) progressively and continuously adding said acid, this remaining amount of said alcohol of general formula II and the remaining amount of metallic nitrite of general formula III to this base stock.
9. Procédé selon la revendication 1 , caractérisé en ce que l'on assèche de manière continue le produit formé de formule générale I sur une colonne de tamis moléculaire ou de potasse.9. Method according to claim 1, characterized in that the product formed of general formula I is continuously dried over a column of molecular sieve or potassium hydroxide.
10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que R représente le groupe n-butyle ou isoamyle.10. Method according to any one of the preceding claims, characterized in that R represents the n-butyl or isoamyl group.
11. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'acide fort est l'acide chlorhydrique ou sulfurique.11. Method according to any one of the preceding claims, characterized in that the strong acid is hydrochloric or sulfuric acid.
12. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le nitrite alcalin est du nitrite de sodium ou de potassium. 12. Method according to any one of the preceding claims, characterized in that the alkali nitrite is sodium or potassium nitrite.
EP01921463A 2000-04-03 2001-04-03 Method for preparing alkyl nitrites Withdrawn EP1268394A1 (en)

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FR0004231A FR2807035B1 (en) 2000-04-03 2000-04-03 PROCESS FOR THE PREPARATION OF ALKYL NITRITES
FR0004231 2000-04-03
PCT/FR2001/000999 WO2001074754A1 (en) 2000-04-03 2001-04-03 Method for preparing alkyl nitrites

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AU (1) AU2001248452A1 (en)
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