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

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• 1978
  • 1978-06-01 CA CA304,629A patent/CA1101431A/fr not_active Expired
  • 1978-06-05 US US05/912,356 patent/US4182731A/en not_active Expired - Lifetime
  • 1978-06-13 DE DE7878100145T patent/DE2860043D1/de not_active Expired
  • 1978-06-13 EP EP78100145A patent/EP0000140B1/fr not_active Expired
  • 1978-06-16 JP JP7226878A patent/JPS549248A/ja active Granted

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