EP0000140B1 - Procédé de préparation de solutions aqueuses ou de dispersions aqueuses finement divisées de sels de polyényltriarylphosphonium - Google Patents

Procédé de préparation de solutions aqueuses ou de dispersions aqueuses finement divisées de sels de polyényltriarylphosphonium Download PDF

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Publication number
EP0000140B1
EP0000140B1 EP78100145A EP78100145A EP0000140B1 EP 0000140 B1 EP0000140 B1 EP 0000140B1 EP 78100145 A EP78100145 A EP 78100145A EP 78100145 A EP78100145 A EP 78100145A EP 0000140 B1 EP0000140 B1 EP 0000140B1
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EP
European Patent Office
Prior art keywords
solution
aqueous
solutions
steam
solvent
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EP78100145A
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German (de)
English (en)
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EP0000140A1 (fr
Inventor
Bernhard Dr. Schulz
Paul Dr. Grafen
Hans-Ulrich Dr. Scholz
Hans Dr. Grassner
Werner Dr. Reif
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BASF SE
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BASF SE
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Priority claimed from DE19772727384 external-priority patent/DE2727384A1/de
Priority claimed from DE19772729974 external-priority patent/DE2729974C3/de
Application filed by BASF SE filed Critical BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5428—Acyclic unsaturated phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)

Definitions

  • the present invention relates to a process for the preparation of aqueous solutions or aqueous finely divided dispersions of polyenyltriarylphosphonium salts of the general formula 1 in which R represents an aliphatic, cycloaliphatic-aliphatic or aromatic-aliphatic polyenyl radical having 5 to 20 carbon atoms, X denotes the anion equivalent of a strong acid and Ar denotes an aryl radical, in particular the phenyl radical.
  • Some of the compounds I are directly suitable as pesticides, e.g. to combat water snails, others serve as intermediates for organic syntheses, especially in the carotenoid field (see, inter alia, DT-PS 1 203 264 and 1 046 046). Both for immediate use and for use in further syntheses, e.g. For the production of synmetric carotenoids according to DT-OS 2 505 869, aqueous solutions or aqueous, finely divided dispersions of the compounds I are often recommended.
  • Lower aliphatic alcohols, lower carboxylic acids, such as HCOOH or CH 3 COOH, acetone, or the customary water-insoluble solvents, such as benzene, toluene, tetrahydrofuran, acetonitrile, methylene chloride, chloroform, diethyl ether, dioxane and esters, such as methyl and Diethyl acetate is known, ie solutions of I in the solvents mentioned are obtained in the customary production methods.
  • the best yields of I are obtained when using lower alcohols, such as ethanol, isopropanol, isobutanol, n-propanol, n-butanol and especially methanol as the solvent.
  • lower alcohols such as ethanol, isopropanol, isobutanol, n-propanol, n-butanol and especially methanol as the solvent.
  • solutions of the lower alcohols mentioned, in particular methanolic I solutions are preferably used as starting solutions for the preparation of aqueous I solutions.
  • the conversion of solutions of I in one of the other solvents mentioned above into aqueous i solutions is also of interest.
  • GB-PS 1 059 673 which relates to a process for the preparation of polyene compounds, also gave no indication of an advantageous way of producing aqueous solutions or finely divided aqueous dispersions of polyentriarylphosphonium salts.
  • this process can be carried out particularly well continuously by passing the organic solution from I continuously from above into a column, preferably into a packed column, and bringing it into contact with the water vapor in countercurrent, in this case part of the water vapor can condense and the aqueous solution of I formed continuously withdrawn from the lower part of the column.
  • the metering of the I solution and of the water vapor can easily be set up in such a way that the desired aqueous I solution can be drawn off directly as a bottom product in the form of a homogeneous, viscous solution.
  • the hot bottom product is advantageously continuously transferred to a stirred tank. Cooling and stirring generally gives this hot, aqueous I solution a dispersion which contains finely divided, crystalline phosphonium salt, dispersed in water or in aqueous phosphonium salt solution.
  • the melting points or decomposition points of the triarylphosphonium salts in particular the Triphenylphosphoniumhydrogensulfate about 100 ° C (SS-Jonylidentriphenylphosphoniumhydrogensulfat for example, melts at 183-85 ° C with decomposition, Axerophthyltriphenylphosphoniumhydrogensulfat at 188-190 0 C with decomposition) and that the The solubility of the triarylphosphonium salts in water is low, especially at room temperature.
  • the process according to the invention can be carried out batchwise or continuously. Surprisingly, no disruptive foam formation can be observed either in a batch or in a continuous process variant.
  • the solution of in the organic solvent in a reaction vessel is kept at a temperature just below the boiling point of the solvent, water vapor is passed into it and the solvent evaporating therefrom, other steam-volatile compounds originating from the synthesis of I and a portion distill off the water vapor from the reaction vessel.
  • the temperature of the input solution should be below the boiling point of the solvent; the bottom temperature should be about 100 ° C; the feed is to be regulated in such a way that the solvent largely evaporates on the packing by dissolving through the column.
  • a small column height is sufficient for a low feed, and the column capacity must be correspondingly large for larger throughputs.
  • the suitable operating conditions can easily be determined on the basis of a few preliminary tests, so that detailed explanations for this are unnecessary. This also applies to working at lower or higher pressure than normal pressure.
  • the cycloaliphatic radical can also be replaced by an aromatic radical, such as phenyl or alkylated, especially methylated phenyl.
  • the type of anion in the polyenyltriarylphosphonium salt is also irrelevant to the success of the process according to the invention.
  • the phosphonium salts of strong acids such as N Z S0 4 , HCl, HBr, HCOOH and H 3 P0 4 are used, so that X in I for HSO 4 ⁇ , CI-, Br-, HCOO ⁇ or H 2 PO 4 ⁇ , preferably stands for HS0 4 9 .
  • the process according to the invention is suitable for converting I solutions into all organic solvents which, when water vapor is blown in, have a loading percentage of the water vapor with organic solvent of 10% and more and which have a boiling point of about 50 to 150 ° C.
  • the process is of particular importance for those solvents in which the polyenyltriarylphosphonium salts can be prepared in particularly good yields and in which the phosphonium salts are readily soluble.
  • Lower alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol and iso-butanol, may be mentioned; lower carboxylic acids, such as HCOOH and acetic acid as well as acetone and methylene chloride.
  • the method according to the invention is used with particular advantage for checking methanolic solutions of polyenyltriarylphosphonium salts.
  • the solutions of I in organic solvents are prepared by customary methods from triarylphosphine, in particular triphenylphosphine, a strong acid such as HCl. HBr, HCOOH, H 3 P0 4 or in particular sulfuric acid and a compound RX, where X is preferably a free hydroxyl group or a hydroxyl group esterified with a lower carboxylic acid such as acetic acid.
  • triarylphosphine in particular triphenylphosphine
  • a strong acid such as HCl. HBr, HCOOH, H 3 P0 4 or in particular sulfuric acid
  • RX preferably a free hydroxyl group or a hydroxyl group esterified with a lower carboxylic acid such as acetic acid.
  • RX is preferably a free hydroxyl group or a hydroxyl group esterified with a lower carboxylic acid such as acetic acid.
  • Other methods of producing triarylphosphonium salts can of course also be
  • the amount and temperature of the required water vapor depend on the circumstances of the individual case. Is it e.g. pure methanolic I solutions, about 1 - 3 kg of water vapor at 100 ° C are required to remove 1 kg of methanol. This value decreases with increasing temperature and becomes larger with falling temperature and under reduced pressure, so that concentrated aqueous I solutions are obtained when using higher steam temperatures. If the methanolic I solutions still contain impurities (usually about 1 to 10 mole percent of 1), additional steam is required to drive them out. On the basis of this information, the person skilled in the art can determine the optimum process conditions, including the setting of the reflux ratio, by means of a few preliminary tests. With a suitable design of the column, e.g. distill off an 80-90 percent methanol over the top of the column.
  • aqueous f solutions or finely divided dispersions of I in water obtained as process products can be used for further reactions, for example for the production of symmetrical carotenoids, such as ⁇ -carotene or for the production of vitamin A or used according to the usual methods, for example as a pesticide.
  • the methylene chloride can be used again after the water has been separated off and distilled.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (3)

1. Procédé pour la transformation en solutions aqueuses ou en dispersions aqueuses finement divisées avec une teneur résiduelle limitée en solvant organique de solutions d'environ 10 à 70 % en poids dans un solvant organique de sels de polyényl-triaryl-phosphonium de la formule générale
Figure imgb0008
dans laquelle le symbole R désigne un groupe polyényle aliphatique, cycloaliphatique-aliphatique ou aromatique-aliphatique en C5 à C2o, le symbole X l'équivalent anionique d'un acide fort et le symbole Ar un groupe aryle, caractérisé en ce que le solvant organique, ainsi que les produits entraînables à la vapeur d'eau, formés lors de la synthèse du composé de la formule I, sont entrainés à la vapeur d'eau de la solution maintenue entre 30 et 120°C, une fraction de la vapeur étant condensée pour l'obtention de la solution aqueuse ou dispersion aqueuse finement divisée du composé de la formule I.
2. Procédé suivant la revendication 1, caractérisé en ce que la solution organique d'un composé de la formule 1 est introduite en continu en tête d'une colonne, traversée en continu d'un contre-courant de vapeur d'eau, dont une fraction est condensée, la solution aqueuse du composé de la formule I étant soutirée en continu à la base de la colonne.
3. Procédé suivant l'une quelconque des revendications 1 et 2, caractérisé en ce que la solution organique de départ du composé de la formule I est une solution méthanolique.
EP78100145A 1977-06-18 1978-06-13 Procédé de préparation de solutions aqueuses ou de dispersions aqueuses finement divisées de sels de polyényltriarylphosphonium Expired EP0000140B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2727384 1977-06-18
DE19772727384 DE2727384A1 (de) 1977-06-18 1977-06-18 Verfahren zur herstellung von waessrigen loesungen von polyenyltriarylphosphoniumsalzen
DE19772729974 DE2729974C3 (de) 1977-07-02 1977-07-02 Verfahren zur Herstellung von wäßrigen Lösungen bzw. feinteiligen wäßrigen Dispersionen von Polyenyltriarylphosphoniumsalzen
DE2729974 1977-07-02

Publications (2)

Publication Number Publication Date
EP0000140A1 EP0000140A1 (fr) 1979-01-10
EP0000140B1 true EP0000140B1 (fr) 1980-07-23

Family

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EP78100145A Expired EP0000140B1 (fr) 1977-06-18 1978-06-13 Procédé de préparation de solutions aqueuses ou de dispersions aqueuses finement divisées de sels de polyényltriarylphosphonium

Country Status (5)

Country Link
US (1) US4182731A (fr)
EP (1) EP0000140B1 (fr)
JP (1) JPS549248A (fr)
CA (1) CA1101431A (fr)
DE (1) DE2860043D1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5166445A (en) * 1989-02-10 1992-11-24 Hoffman-La Roche Inc. Method for the manufacture of carotinoids and the novel intermediates
DE4344148A1 (de) * 1993-12-23 1995-08-24 Basf Ag Verfahren zur Herstellung von 9-(Z)-Retinsäure
DE19734446A1 (de) * 1997-08-08 1999-02-11 Basf Ag Verfahren zur Herstellung von Phosphoniumsalzen
DE19838636A1 (de) 1998-08-26 2000-03-02 Basf Ag Carotinoid-Formulierungen, enthaltend ein Gemisch aus beta-Carotin, Lycopin und Lutein
DE19841930A1 (de) 1998-09-14 2000-03-16 Basf Ag Stabile, pulverförmige Lycopin-Formulierungen, enthaltend Lycopin mit einem Kristallinitätsgrad von größer 20%
DE10009459C1 (de) 2000-03-02 2001-06-07 Basf Ag Verfahren zur Herstellung von Phosphoniumsalzen
DE10129403A1 (de) * 2001-06-19 2003-01-02 Basf Ag Verfahren zur Reinigung von Phosphoniumsalzen
US6730812B2 (en) * 2002-02-06 2004-05-04 Iowa State University Research Foundation, Inc. Solvent-free mechanochemical preparation of phosphonium salts, phosphorus ylides, and olefins
DE10359434A1 (de) * 2003-12-17 2005-07-21 Basf Ag Verfahren zur Herstellung von Phosphoniumsalzen
DE10359433A1 (de) * 2003-12-17 2005-07-21 Basf Ag Verfahren zur Herstellung von Vitamin A-Acetat

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2905717A (en) * 1956-06-29 1959-09-22 Basf Ag Production of quaternary phosphonium halides
US2950321A (en) * 1957-09-03 1960-08-23 Basf Ag Production of beta-ionylidene-ethyltriaryl phosphonium halides
US2945069A (en) * 1958-01-31 1960-07-12 Eastman Kodak Co Synthesis of beta-carotene
NL293043A (fr) * 1962-05-23
BE639829A (fr) * 1962-11-16
NL124639C (fr) * 1963-05-24
US3347932A (en) * 1964-02-11 1967-10-17 Eastman Kodak Co Synthesis of quaternary phosphonium salts
US3408414A (en) * 1964-12-04 1968-10-29 Hoffmann La Roche Novel processes and intermediates

Also Published As

Publication number Publication date
CA1101431A (fr) 1981-05-19
US4182731A (en) 1980-01-08
JPS549248A (en) 1979-01-24
DE2860043D1 (en) 1980-11-13
JPS6228798B2 (fr) 1987-06-23
EP0000140A1 (fr) 1979-01-10

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