EP0000140A1 - 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
EP0000140A1
EP0000140A1 EP78100145A EP78100145A EP0000140A1 EP 0000140 A1 EP0000140 A1 EP 0000140A1 EP 78100145 A EP78100145 A EP 78100145A EP 78100145 A EP78100145 A EP 78100145A EP 0000140 A1 EP0000140 A1 EP 0000140A1
Authority
EP
European Patent Office
Prior art keywords
solutions
aqueous
solution
water vapor
salts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP78100145A
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German (de)
English (en)
Other versions
EP0000140B1 (fr
Inventor
Bernhard Dr. Schulz
Paul Dr. Grafen
Hans-Ulrich Dr. Scholz
Hans Dr. Grassner
Werner Dr. Reif
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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
Publication of EP0000140A1 publication Critical patent/EP0000140A1/fr
Application granted granted Critical
Publication of EP0000140B1 publication Critical patent/EP0000140B1/fr
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Classifications

    • 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 I.
  • 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
  • Ar denotes an aryl radical, in particular the phenyl radical.
  • Some of the compounds I are directly suitable as pesticides, for example for controlling water snails, others serve as intermediates for organic syntheses, in particular 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, such as for the preparation of synmetric carotenoids according to the DT-OS 2 505 869, aqueous solutions or aqueous, finely divided dispersions of the compounds I are frequently recommended.
  • 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 I in the lower alcohols mentioned, in particular, are preferred as starting solutions for the preparation of aqueous I solutions special methanolic I solutions are used.
  • the conversion of solutions of I in one of the other solvents mentioned above into aqueous I solutions is also of interest.
  • 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 steam in countercurrent; this allows a part of the water vapor to condense and continuously draws off the aqueous solution of I formed from the lower part of the column.
  • the dosage 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 the decomposition points of the triarylphosphonium salts, in particular the triphenylphosphonium hydrogen sulfates are above 100 ° C.
  • ß-Jonylidentriphenylphosphonium hydrogen sulfate melts, for example, at 183-85 ° C. with decomposition, axerophthyltriphenylphosphonium hydrogenation and the decomposition at 188–190 ° C. sulfate at 188-190 ° C. sulfate at 188-190 ° C. sulfate at 188–19 ° C. sulfate at 188-190 ° C. sulfate at 188–190 ° C. sulfate at 188–190 ° C.
  • 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 I in the organic solvent is kept in a reaction vessel at a temperature just below the boiling point of the solvent, water vapor is introduced into it and the solvent evaporating therefrom, other compounds derived from the synthesis of I, and volatile compounds and one Distill off part of 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 small feed, and the column capacity must be correspondingly larger for larger throughputs.
  • the suitable operating conditions can easily be determined on the basis of a few preliminary tests, so that detailed explanations are not necessary. 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 H 2 S0 4 , HCl, HBr, HCOOH and H 3 P0 4 are used, so that X in I for HSO 4 ⁇ , Cl - , Br - , HCOO ⁇ or H 2 PO 4 ⁇ , preferably stands for HSO 4 ⁇ .
  • 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 proportion 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, isopropanol, n-butanol and isobutanol, 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 HC1, HBr, HCOOH, H 3 PO 4 or in particular sulfuric acid and a compound RX, where X is preferably a free hydroxyl group or is a hydroxyl group esterified with a lower carboxylic acid such as acetic acid.
  • triarylphosphine in particular triphenylphosphine
  • a strong acid such as HC1, HBr, HCOOH, H 3 PO 4 or in particular sulfuric acid
  • RX preferably a free hydroxyl group or is a hydroxyl group esterified with a lower carboxylic acid such as acetic acid.
  • RX is preferably a free hydroxyl group or is a hydroxyl group esterified with a lower carboxylic acid such as acetic acid.
  • Other methods of producing triarylphosphonium salts can of course also be used
  • the amount and temperature of the required water vapor depend on the circumstances of the individual case. For example, if it is 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 I), additional steam is required to drive them out. On the basis of this information, the person skilled in the art can determine the optimal process conditions, including the setting of the reflux ratio, by means of a few preliminary tests. By By suitable design of the column, for example, 80-90 percent methanol can be distilled off over the top of the column.
  • aqueous I solutions or finely divided dispersions of I in water obtained as process products can be used for further reactions, e.g. used for the production of symmetrical carotenoids, such as the ß-carotene or for the production of vitamin A or by the usual methods, e.g. can be used as pesticides.
  • the methanolic phosphonium salt solution obtained in accordance with FIG. 1a was added in 90 minutes from above to a packed column made of glass 50 cm long and 3 cm in diameter.
  • the column was filled with glass Raschig rings and insulated. At the lower end of the column, 3 900 g of water vapor were blown in over the course of 90 minutes.
  • the aqueous phosphonium salt solution or suspension was drained from the bottom of the column via a siphon and collected in a stirred flask. About 1,400 g of an easily stirrable, aqueous suspension were obtained which contained 497 g of ⁇ -jonylidene-ethyl-triphenylphosphonium hydrogen sulfate. This corresponds to a loss of 95% of theory.
  • the methanolic solution obtained according to 2a was added in 60 minutes from above to the packed column described in Example 1. At the lower end of the column, 2,200 g of water vapor were blown in over the 60 minutes. About 1,000 g of bottom effluent were obtained.
  • the aqueous solution of axerophthyltriphenylphosphonium hydrogen sulfate obtained was converted to ⁇ -carotene according to Example 6 of DOS 25 05 869. After isomerization of the product obtained in heptane, alltrans-ß-carotene was obtained in 70% yield, based on the vitamin A acetate used.
  • 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)
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
DE2729974 1977-07-02
DE19772729974 DE2729974C3 (de) 1977-07-02 1977-07-02 Verfahren zur Herstellung von wäßrigen Lösungen bzw. feinteiligen wäßrigen Dispersionen von Polyenyltriarylphosphoniumsalzen

Publications (2)

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

Family

ID=25772164

Family Applications (1)

Application Number Title Priority Date Filing Date
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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0659739A1 (fr) * 1993-12-23 1995-06-28 BASF Aktiengesellschaft Procédé pour la préparation de l'acide 9-(Z)-rétinoique
US6235315B1 (en) 1998-09-14 2001-05-22 Basf Aktiengesellschaft Stable, pulverulent lycopene formulations, comprising lycopene having a degree of crystallinity of greater than 20%

Families Citing this family (8)

* 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
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
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
AU2003208999A1 (en) * 2002-02-06 2003-09-02 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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1059673A (en) * 1962-11-16 1967-02-22 Hoffmann La Roche Process for the preparation of polyene compounds

Family Cites Families (7)

* 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
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1059673A (en) * 1962-11-16 1967-02-22 Hoffmann La Roche Process for the preparation of polyene compounds

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0659739A1 (fr) * 1993-12-23 1995-06-28 BASF Aktiengesellschaft Procédé pour la préparation de l'acide 9-(Z)-rétinoique
US5504230A (en) * 1993-12-23 1996-04-02 Basf Aktiengesellschaft Preparation of 9-(Z)-retinoic acid
US6235315B1 (en) 1998-09-14 2001-05-22 Basf Aktiengesellschaft Stable, pulverulent lycopene formulations, comprising lycopene having a degree of crystallinity of greater than 20%
EP0986963B1 (fr) 1998-09-14 2016-12-07 Basf Se Formulations de lycopène stable et pulvérulente contenant de lycopène avec un taux de crystallisation de plus de 20%

Also Published As

Publication number Publication date
JPS549248A (en) 1979-01-24
DE2860043D1 (en) 1980-11-13
EP0000140B1 (fr) 1980-07-23
US4182731A (en) 1980-01-08
JPS6228798B2 (fr) 1987-06-23
CA1101431A (fr) 1981-05-19

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