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EP0000061B1 - Dérivés d'acide carboxylique contenant du phosphore, procédé pour leur préparation et leur utilisation - Google Patents

Dérivés d'acide carboxylique contenant du phosphore, procédé pour leur préparation et leur utilisation Download PDF

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Publication number
EP0000061B1
EP0000061B1 EP78100104A EP78100104A EP0000061B1 EP 0000061 B1 EP0000061 B1 EP 0000061B1 EP 78100104 A EP78100104 A EP 78100104A EP 78100104 A EP78100104 A EP 78100104A EP 0000061 B1 EP0000061 B1 EP 0000061B1
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Prior art keywords
radicals
compounds
optionally
alkyl
acid
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.)
Expired
Application number
EP78100104A
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German (de)
English (en)
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EP0000061A1 (fr
Inventor
Horst Dieter Dr. Thamm
Fritz Dr. Linke
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Hoechst AG
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Hoechst AG
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Classifications

    • 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
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4025—Esters of poly(thio)phosphonic acids
    • C07F9/4046—Esters of poly(thio)phosphonic acids containing carboxylic acid or carboxylic acid derivative substituents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • 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
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/305—Poly(thio)phosphinic acids
    • 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
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3235—Esters of poly(thio)phosphinic acids
    • 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
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/3869—Polyphosphonic acids containing carboxylic acid or carboxylic acid derivative substituents
    • 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
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5304—Acyclic saturated phosphine oxides or thioxides
    • C07F9/5308—Acyclic saturated phosphine oxides or thioxides substituted by B, Si, P or a metal
    • C07F9/5312—Acyclic saturated phosphine oxides or thioxides substituted by B, Si, P or a metal substituted by a phosphorus atom
    • 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
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5329—Polyphosphine oxides or thioxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof

Definitions

  • diphosphonates and polyphosphonates are to be used in the form of the Sn (II) salts in oral compositions for preventing tooth decay and tartar formation in oral care products, chewing gums, etc.
  • esters of 3,3-diphosphonopimelic acid d.i. those di-adducts of the formula given for this purpose, in which A means only the — optionally halogen-substituted — alkyl radicals, but not H and the alkali metal or ammonium ions.
  • the esters can be transesterified to other esters in a known manner.
  • the free acid and the alkali and ammonium salts are obtained from the esters in a likewise known manner by acidic or alkaline saponification.
  • the products obtained in this way are obtained in a suitable purity or can be easily cleaned by distillation after by-products have been removed.
  • Suitable metalating agents are the alkali metals and their hydrides, in particular Li, Na, LiH, NaH.
  • Strong bases such as e.g. Alkaline alcoholates, hydrides, amides, quaternary ammonium hydroxides used.
  • Alkali alcoholates, alkali hydrides and amides are particularly preferred.
  • the Na and K compounds are particularly preferred.
  • a solvent or diluent are all organic solvents which are inert under the reaction conditions, such as aliphatic and aromatic hydrocarbons, e.g. n-pentane, n-hexane, decane, toluene, xylene, ether such as e.g. Tetrahydrofuran, diethyl ether,
  • the reaction temperatures can be varied within a wide range; generally one works between about + 20 ° and + 100 ° C, especially between about + 40 ° and + 80 ° C. Since the addition reaction is exothermic, good cooling may be required.
  • An excess of component III up to about 10% is possible; Larger quantities are possible, but without advantage.
  • the basic catalyst e.g. sodium methylate in methanolic solution
  • the basic catalyst generally about 0.01 to 0.25 mol per mol of compound II, is added.
  • the reaction temperature or the reaction rate can be regulated both by external cooling and by the metering rate of the catalyst.
  • the adducts I are formed in sufficient purity in accordance with the process according to the invention, so that they can be directly processed further after volatile components have been distilled off in vacuo.
  • the removal of the catalyst components is expediently carried out by treatment with water / activated carbon and is necessary when using these adducts as plasticizers for PVC.
  • the substituted carboxylic acids according to the invention optionally dissolved in hydrochloric acid or water, are present and can be obtained in anhydrous form by distilling off water and / or hydrochloric acid in vacuo and at temperatures up to about + 150.degree.
  • Acidolysis can also be particularly advantageously analogous to the process proposed in patent application P 2719415.6 by heating with lower aliphatic.
  • Carboxylic acids HCOOH, CH 3 COOH, C 2 H 5 COOH etc.
  • benzoic acid HCOOH, CH 3 COOH, C 2 H 5 COOH etc.
  • the compounds covered by Formula 1 can be converted into one another by known operations.
  • R 2 COOH
  • R 2 COOH
  • R2 CN
  • R2 CN
  • the (substituted) carboxamides of the formula 1 can be obtained in a technically simple manner under gentle conditions by known processes from the analogous carboxylic acid nitriles by reaction with hydrogen peroxide / sodium hydroxide solution. Likewise, the reaction of the substituted carboxylic acid esters with ammonia or substituted amines at 20 ° -100 ° C, optionally under pressure, leads to the unsubstituted or substituted carboxamides.
  • the compounds of the formula I are versatile, valuable products.
  • the acids and salts of the formula I can be used as gypsum binders or complexing agents, in particular for metal ions such as iron or alkaline earth metal ions. They can therefore be used for water softening. Compounds with m + n + p + q ⁇ 2 are preferred for this.
  • the compounds of the formula also have favorable properties as flame retardants, especially in the primer of pile carpets.
  • Example (1) 10 g of a 33% are slowly added to a mixture of 114 g (0.5 mol) of diethyl methane-dimethylphosphinoxidophosphonate, 200 ml of absolute dioxane and 100 g (1.0 mol) of ethyl acrylate at 40 ° C. sodium methoxide solution dropped into methanol. After appropriate work-up, 197 g of a colorless liquid (92% of theory) remain.
  • Example (3) Analogously to Example (3), 114 g (0.5 mol) of methane-dimethylphospinoxido-phosphonic acid diethyl ester in 200 ml of absolute dioxane with 53 g (1.0 mol) of acrylonitrile and 10 g of a 33% sodium methylate solution in methanol at a maximum of 60 ° C implemented. After working up, 160 g (96% of theory) of a yellowish oil remain.
  • Example No. 11 As in Example No. 11, 88 g (0.25 mol) of methane-di- (phenylphosphinic acid ethyl ester), 50 g (0.5 mol) of ethyl acrylate and 2 g of 33% NaOCH 3 / CH 3 OH solution are reacted. After working up, 125 g of a yellow oil (90.5% of theory) are obtained.
  • Test method Vicat method according to DIN 1168
  • the squeezing effect is approx. 75%. After predrying at 100 ° ⁇ 110 ° C, the mixture is condensed at 170 ° C for 4 minutes. It is then washed with 2.3 g / l of soda for 5 minutes at 90 ° C and rinsed very well warm and cold until free of alkali and dried again at 100 ° C.
  • the cotton fabric treated in this way shows very good flame-retardant properties, which are retained even after three further machine washings with 3 g / l of a commercially available detergent.
  • the untreated cotton fabric continues to burn after the flame has been removed.
  • the treated fabric shows a burn-in length of 6 cm after washing and 8 cm after a three-time machine wash.
  • the handle After washing, the handle is soft and flowing.
  • the squeezing effect on a two-roll foulard is approx. 70%. After predrying at 100 ° C, condensation is carried out at 150 ° C for 5 minutes.
  • the needle punched fabric treated in this way is then dried at 145 ° C. for 30 minutes.
  • the needle punched fabric shows good dimensional stability and good unrolling ability.
  • the needle fleece shows very good flame retardant properties according to DIN 54 333.
  • test specimen of the needle felt described above with a weight of 750 g per square meter is only treated with 300 g / l of the 40% plastic dispersion, it will continue to burn in a broad direction after the flame has been removed.
  • the flame front runs through the test section of 10 cm in a time of 2 minutes and 55 seconds.
  • the needle-punched non-woven fabric according to the invention does not continue to burn after the test flame has been removed. Outside the test section, an afterglow of only 8-10 seconds could be detected. After 3 shampoos, the flame retardant properties of the needle fleece are fully retained. The post-flame time increased to only 1 minute and 15 seconds.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (8)

1. Dérivés d'acides carboxyliques phosphorés répondant à la formule générale 1
Figure imgb0051
dans laquelle les R représentent chacun, indépendamment les uns des autres:
un atome d'hydrogène,
― un radical alkyle en C1―C20 ou un radical alcényle en C2―C8, chacun des radicaux de ces deux types pouvant porter un ou des substituants, de préférence au plus trois, plus particulièrement un seul qui est un halogène, surtout CI ou Br,
- un radical cycloalkyle en C5 ou C6,
- un radical phényle ou un radical phényl-(C1―C4)alkyle, chacun des radicaux de ces deux: derniers types pouvant porter un ou des substituants sur le noyau, de préférence au plus trois, qui sont pris dans l'ensemble constitué par les halogènes, de préférence CI ou Br, et les alkyles en C1―C4, ou
- un cation de métal alcalin ou d'ammonium, de préférence Na ou K,
mais R ne pouvant représenter H ou un cation dans le cas où l'indice m, n, p ou q correspondant est égal à 0,
R1 représente H ou un radical alkyle en C1―C4,
R2 représente CN, COOR4, CONR5R6 ou CONH2-x(CH2OH)x (l'indice x étant égal à 1 ou à 2),
R3 représente H ou un radical
Figure imgb0052
dans lequel R'1 et R'2 ont des significations telles que celles qui ont été données pour R1 et R2,
R4 a des significations identiques à celles qui ont été données pour R,
R5 et R6 représentent chacun un atome d'hydrogène, un radical alkyle en C1―C20 ou un radical phényle, chacun des radicaux de ces deux derniers types pouvant porter un substituant, de préférence au plus trois, pris dans l'ensemble constitué par les halogènes (de préférence CI et Br) et les radicaux alkyles en C1―C4, et
m, n, p et q représentent chacun, indépendamment les uns des autres le nombre 0 ou le nombre 1, avec la restriction que, dans le cas où R2 représente CN ou COOR4, les indices m, n, p et q ne soient pas tous égaux à 1 et que, dans le cas où R désigne un radical C6H5 et m = n = p = q = 0, R3 ne soit pas l'hydrogène.
2. Composés selon la revendication 1, dans lesquels R, R4, R5 et R6 ne peuvent représenter chacun que H ou un radical alkyle.
3. Composés selon l'une des revendications 1 et 2, dans lesquels R, R1, R4, R5 et R6 représentent chacun un radical alkyle en C,-C4, plus particulièrement un radical méthyle ou éthyle, ou un radical chloréthyle.
4. Composés selon l'une quelconque des revendications 1 à 3, dans lesquels R2 et éventuellement aussi R'2 représentent CN, CONH2 ou CONH2-x(CH2OH)x, l'indice x étant égal à 1 ou à 2.
5. Procédé de préparation de composés de formule I, procédé caractérisé en ce qu'on fait réagir des composés de formule générale
Figure imgb0053
dans lesquels R' = R mais # H, m, n, p et q représentent chacun, indépendamment les uns des autres, le nombre 0 ou le nombre 1 et Me représente l'hydrogène ou un atome de métal alcalin (de préférence Li ou Na), éventuellement dans un solvant inerte, avec des composés de formule
Figure imgb0054
dans lesquels R1 a la signification donnée à la revendication 1 et R7 représente CN, COOR4 ou CONR5R6, de préférence CN ou COOR4, éventuellement (lorsque Me = H) en présence de catalyseurs très basiques, à des températures d'environ 0 à 140°C, on saponifie un composé ainsi obtenu renfermant un groupement C-Me (Me = métal alcalin) de manière à la convertir en un composé renfermant un groupement C-H, et éventuellement, mais obligatoirement lorsque m = n = p = q = 1, on transforme un groupe nitrile ou ester carboxylique, de manière connue, en un autre groupe R2, de préférence en un groupe carbamoyle éventuellement substitué à l'azote, et, le cas échéant, on méthylole avec du formaldéhyde le groupe carbamoyle ainsi obtenu.
6. Utilisation des composés spécifiés à l'une quelconque des revendications 1 à 4 dans lesquels R et R4 ne représentent que les radicaux organiques indiqués dans ces revendications, comme plastifiants pour matières plastiques, plus spécialement pour le polychlorure de vinyle.
7. Utilisation des composés selon la revendication 1 dans lesquels R et R4 représentent H, des ions de métaux alcalins et/ou des ions d'ammonium, comme retardateurs de prise pour le plâtre ou comme complexants pour ions métalliques.
8. Utilisation des composés selon la revendication 1 dans lesquels les R représentent des radicaux alkyles en C1―C20 éventuellement halogénés, et R2 ainsi qu'éventuellement R2 représentent CONH2-x(CH2OH)x (x = 1 ou 2), pour l'apprêtage ignifuge de matières contenant de la cellulose, plus spécialement de textiles.
EP78100104A 1977-06-14 1978-06-06 Dérivés d'acide carboxylique contenant du phosphore, procédé pour leur préparation et leur utilisation Expired EP0000061B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH7299/77 1977-06-14
CH729977 1977-06-14

Publications (2)

Publication Number Publication Date
EP0000061A1 EP0000061A1 (fr) 1978-12-20
EP0000061B1 true EP0000061B1 (fr) 1980-10-15

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EP (1) EP0000061B1 (fr)
JP (1) JPS545922A (fr)
DE (1) DE2860216D1 (fr)
IT (1) IT1096642B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3027040A1 (de) * 1980-07-17 1982-02-25 Hoechst Ag, 6000 Frankfurt Dimethylphosphinyl-alkanphosphonsaeuren, ein verfahren zu ihrer herstellung und ihre verwendung als gipsabbindeverzoegerer
DE3225469A1 (de) * 1982-07-05 1984-01-05 Schering AG, 1000 Berlin und 4709 Bergkamen Diphosphonsaeure-derivate und diese enthaltende pharmazeutische praeparate
DE3512536A1 (de) * 1985-04-06 1986-10-16 Boehringer Mannheim Gmbh, 6800 Mannheim Neue diphosphonsaeure-derivate, verfahren zu deren herstellung und diese verbindungen enthaltende arzneimittel
GB9615497D0 (en) 1996-07-24 1996-09-04 Exxon Chemical Patents Inc Materials for use in oils and processes for their manufacture
WO2003021031A1 (fr) * 2001-09-01 2003-03-13 Rhodia Consumer Specialties Limited Composes phosphores

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1768759A1 (de) * 1968-06-27 1972-01-13 Procter & Gamble Zinnsalze von Phosphonsaeuren
DE2602030C2 (de) * 1976-01-21 1983-12-01 Henkel KGaA, 4000 Düsseldorf Diphosphonoalkancarbonsäuren und Verfahren zu deren Herstellung
NL7711307A (nl) * 1976-10-19 1978-04-21 Hoechst Ag Fosforcarbonzuurverbindingen en hun bereiding.

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EP0000061A1 (fr) 1978-12-20
DE2860216D1 (en) 1981-01-22
IT1096642B (it) 1985-08-26
IT7824481A0 (it) 1978-06-12
JPS545922A (en) 1979-01-17

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