FR2492826A1 - Di:alkoxy:propyl phosphoric acid derivs. - prepd. e.g. from di:alkoxy:propanol and phosphorus pent:oxide - Google Patents
Di:alkoxy:propyl phosphoric acid derivs. - prepd. e.g. from di:alkoxy:propanol and phosphorus pent:oxide Download PDFInfo
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- FR2492826A1 FR2492826A1 FR8017877A FR8017877A FR2492826A1 FR 2492826 A1 FR2492826 A1 FR 2492826A1 FR 8017877 A FR8017877 A FR 8017877A FR 8017877 A FR8017877 A FR 8017877A FR 2492826 A1 FR2492826 A1 FR 2492826A1
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- Prior art keywords
- sep
- mono
- acid
- propyl
- bis
- Prior art date
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 11
- -1 propyl phosphoric acid Chemical compound 0.000 title claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 title description 3
- 125000003545 alkoxy group Chemical group 0.000 title 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title 1
- 229910052698 phosphorus Inorganic materials 0.000 title 1
- 239000011574 phosphorus Substances 0.000 title 1
- 239000002253 acid Substances 0.000 claims abstract description 26
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000032050 esterification Effects 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 150000007530 organic bases Chemical class 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 235000011007 phosphoric acid Nutrition 0.000 claims description 8
- 150000003017 phosphorus Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- CPUDLRLOFJLISR-UHFFFAOYSA-N diethyl(trihydroxy)-$l^{5}-phosphane Chemical compound CCP(O)(O)(O)CC CPUDLRLOFJLISR-UHFFFAOYSA-N 0.000 claims description 3
- 229910006024 SO2Cl2 Inorganic materials 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 235000011180 diphosphates Nutrition 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229910019213 POCl3 Inorganic materials 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 2
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- OELGSAPJHDOXEB-UHFFFAOYSA-N bis(1,3-dipropoxypropan-2-yl) hydrogen phosphate Chemical class CCCOCC(COCCC)OP(O)(=O)OC(COCCC)COCCC OELGSAPJHDOXEB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- IFDLXKQSUOWIBO-UHFFFAOYSA-N 1,3-dichloropropan-1-ol Chemical compound OC(Cl)CCCl IFDLXKQSUOWIBO-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- HJKZADVQTYQZPZ-UHFFFAOYSA-N N1C(=O)N(P(=O)=O)C(=O)C2=C1NC(=O)N2 Chemical class N1C(=O)N(P(=O)=O)C(=O)C2=C1NC(=O)N2 HJKZADVQTYQZPZ-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N octan-4-ol Chemical compound CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- 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)
Abstract
Description
La présente invention concerne de nouveaux acides mono- et bis-(dialcoxy-1,3 propyl-2) phosphoriques répondant à la formule
dans laquelle A est un groupe (ROCH2)2CHO avec R représentant un groupe alkyle et B représente le meme groupe (ROCH2)2CHO ou représente un groupe OH.The present invention relates to novel mono- and bis (1,3-dialkoxypropyl-2) phosphoric acids having the formula
wherein A is a group (ROCH2) 2CHO where R is an alkyl group and B is the same group (ROCH2) 2CHO or is an OH group.
L'invention vise également l'obtention de ces nouveaux acides ainsi que leurs sels minéraux. The invention also aims at obtaining these new acids as well as their mineral salts.
Les acides mono- et di-phosphoriques connaissent ces dernières années, un développement important dans le domaine industriel. Or, la présente invention fournit une série de nouveaux acides intéressants qui n'ont, à la connaissance du demandeur, pas été décrits dans la littérature et qui peuvent être obtenus facilement avec une pureté et un rendement élevés. In recent years, mono- and di-phosphoric acids have been developing in the industrial sector. Now, the present invention provides a series of novel acids of interest which, to the Applicant's knowledge, have not been described in the literature and can easily be obtained with high purity and yield.
De façon générale, le procédé consiste à procéder à une transestérification ou à une estérification d'un dérivé du phosphore avec un alcoxy-alcool, et à isoler le produit désiré. In general, the process involves transesterification or esterification of a phosphorus derivative with an alkoxy alcohol, and isolating the desired product.
Suivant un premier mode de réalisation, le dérivé du phosphore est un acide dialkylphosphoreux et la transestérification avec le dialcoxy-alcool (RoeH2)2CHOH est suivie d'une oxydation puis d'une hydrolyse pour donner l'acide bis (dialcoxy-1,3-propyl 2) phosphorique. According to a first embodiment, the phosphorus derivative is a dialkylphosphorous acid and the transesterification with the dialkoxy alcohol (RoeH2) 2CHOH is followed by an oxidation and then a hydrolysis to give the bis (1,3-dialkoxy) acid. propyl 2) phosphoric acid.
De façon avantageuse, l'oxydation est réalisée par action du chlorure de sulfuryle, SO2C12 et l'acide dialkylphosphoreux est l'acide diéthylphosphoreux. Advantageously, the oxidation is carried out by the action of sulfuryl chloride, SO2C12 and the dialkylphosphorous acid is diethylphosphorous acid.
Le schéma réactionnel est alors le suivant
Suivant un deuxième mode de réalisation, le dérivé du phosphore est l'oxychlorure de phosphore et l'estérification avec l'alcoxy-alcool effectuée en présence d'une base en particulier une base organique tertiaire est suivie d'une hydrolyse, fournissant un mélange de mono et de diacide que l'on sépare. According to a second embodiment, the phosphorus derivative is phosphorus oxychloride and the esterification with the alkoxy alcohol carried out in the presence of a base, in particular a tertiary organic base is followed by hydrolysis, providing a mixture mono and diacid that are separated.
Le schéma réactionnel est le suivant
<tb> <SEP> Cl
<tb> <SEP> (ROCH2)2CH.O-P <SEP> hydrolyse <SEP> b
<tb> <SEP> Cl
<tb> <SEP> / <SEP> OH
<tb> <SEP> (ROCH2) <SEP> 2CH.O-P
<tb> <SEP> POU13 <SEP> OH
<tb> (ROCH2)2CH.OH <SEP> bast
<tb> <SEP> ( <SEP> CH <SEP> CH <SEP> O) <SEP> P-Cl <SEP> hydrolyse
<tb> <SEP> O.
<tb><tb><SEP> Cl
<tb><SEP> (ROCH2) 2CH.OP <SEP> hydrolysis <SEP> b
<tb><SEP> Cl
<tb><SEP> / <SEP> OH
<tb><SEP> (ROCH2) <SEP> 2CH.OP
<tb><SEP> POU13 <SEP> OH
<tb> (ROCH2) 2CH.OH <SEP> bast
<tb><SEP>(<SEP> CH <SEP> CH <SEP> O) <SEP> P-Cl <SEP> hydrolysis
<tb><SEP> O.
<Tb>
<SEP> t <SEP> CH2 <SEP> ) <SEP> 2CH <SEP> . <SEP> O <SEP> )20-OH
<tb>
Suivant un troisième mode de réalisation, le dérivé du phosphore est P205 et l'estérification avec l'alcoxy-alcool est effectuée à l'abri de l'humidité. Cette réaction conduit à un mélange des mono- et di-acides pouvant contenir aussi un phosphate neutre et des impuretés telles que pyrophosphates et polymères. <SEP> t <SEP> CH2 <SEP>) <SEP> 2CH <SEP>. <SEP> O <SEP>) 20-OH
<Tb>
According to a third embodiment, the phosphorus derivative is P205 and the esterification with the alkoxy alcohol is carried out in the absence of moisture. This reaction leads to a mixture of mono- and di-acids which may also contain a neutral phosphate and impurities such as pyrophosphates and polymers.
Les exemples suivants sont donnés à titre illustratif et nullement limitatif. Ils illustrent des composés selon l'invention répondant à la formule générale dans laquelle le symbole R du groupe (ROCH2)2CHO est un groupe butyle, un groupe propyle ou éthyl-2-hexyle sans pour autant que l'invention soit limitée aux produits en cause. The following examples are given for illustrative and not limiting. They illustrate compounds according to the invention corresponding to the general formula in which the symbol R of the group (ROCH2) 2CHO is a butyl group, a propyl group or ethyl-2-hexyl without the invention being limited to the products in question. cause.
EXEMPLE 1
Acide bis-(dibutoxy-1,3-Propyl-2) phosphorique
Bis (Dibutoxy-1,3-Propyl-2) phosphoric acid
<tb> <SEP> a) <SEP> ?re'raratoe <SEP> du <SEP> dfbUtç. <SEP> - <SEP> 1,3 <SEP> - <SEP> PrQtarol <SEP> - <SEP> 2
<tb> 24Y9 <SEP> UgG-a+Ev^ < 26 <SEP> w-2cl <SEP> / <SEP> v <SEP> ;!3Cr <SEP> 2 <SEP> 2 n <SEP> F <SEP> T21taC
<tb> <SEP> - <SEP> ~
<tb>
On dissout à chaud tout en agitant 99 g de soude en pastilles à 90 % (soit 2,23 moles) dans 1665 g de butanol anhydre (soit 22,5 moles). Lorsque la soude est entièrement solubilisée, on laisse refroidir et, à la température ambiante, on coule 139 g de dichloro-1,3-propanol-2 (soit 1,08 mole). La réaction n'est pas exothermique. La coulée terminée, on chauffe au reflux pendant une heure. On observe la formation d'un précipité de chlorure de sodium.On laisse refroidir, on filtre et on chasse l'excès de butanol. On lave le résidu deux fois à l'eau. On extrait à l'éther, on sèche sur du sulfate de magnésium et on chasse l'éther. On distille le résidu ; point d'ébullition :110-112 C/15 mm Hg. On récupère 143 g de produit. Rendement : 65 %.<tb><SEP> a) <SEP>? reraratoe <SEP> of <SEP> dfbUtç. <SEP> - <SEP> 1,3 <SEP> - <SEP> PrQtarol <SEP> - <SEP> 2
<tb> 24Y9 <SEP> UgG-a + Ev <26 <SEP> w-2cl <SEP> / <SEP> v <SEP>;! 3Cr <SEP> 2 <SEP> 2 n <SEP> F <SEP > T21taC
<tb><SEP> - <SEP> ~
<Tb>
99 g of sodium hydroxide in 90% pellets (ie 2.23 mol) are dissolved in hot water in 1665 g of anhydrous butanol (ie 22.5 mol). When the sodium hydroxide is completely solubilized, it is allowed to cool and 139 g of 1,3-dichloro-2-propanol (ie 1.08 mol) are poured in at room temperature. The reaction is not exothermic. When the casting is complete, the mixture is refluxed for one hour. The formation of a precipitate of sodium chloride is observed. It is allowed to cool, is filtered and the excess butanol is removed. The residue is washed twice with water. It is extracted with ether, dried over magnesium sulphate and the ether is removed. The residue is distilled; boiling point: 110-112 ° C./15 mm Hg. 143 g of product are recovered. Yield: 65%.
b) Préparation. de l'acide bis- < dibutoxy-1,3- propyl-2) phosphoreux par transestérification
On met 143 g de dibutoxy-1,3-propanol-2 (soit 0,7 mole) et 48,36 g d'acide diéthylphosphoreux (soit 0,35 mole) sous courant d'argon dans un ballon à distiller avec colonne de Vigreux. On chauffe progressivement jusqu'à environ 1500C dans un bain d'huile et on observe la distillation de l'éthanol. On maintient cette température tant que l'alcool distille puis on l'élève progressivement jusqu'à 1800C. On laisse refroidir et on distille sous vide les produits légers et ceux qui n'ont pas réagi. On récupère 25 g d'éthanol (rendement : 78 %) et 150 g d'acide brut (rendement : 94 %). 143 g of 1,3-dibutoxypropanol-2 (ie 0.7 mole) and 48.36 g of diethylphosphorous acid (ie 0.35 mole) are added under an argon stream in a distillation flask with a column of Vigreux. The mixture is gradually heated to about 1500C in an oil bath and the ethanol distillation is observed. This temperature is maintained as long as the alcohol is distilled and then gradually raised to 1800 ° C. Allowed to cool and vacuum distilled light products and those that have not reacted. 25 g of ethanol (yield: 78%) and 150 g of crude acid (yield: 94%) are recovered.
c) Oxydation et préparation du chlorure d'acide :
On met dans un réacteur 150 g de l'acide cidessus (soit 0,33 mole) et 150 mi de benzène. On refroidit à OOC et on coule goutte à goutte, tout en agitant, une solution de chlorure de sulfuryle préparée à partir de 44,27 g de
SO2Cl2 (soit 0,33 mole) et 50 ml de benzène de façon à maintenir la température entre 0 et 50C La coulée terminée, on laisse remonter la température progressivement puis on dégaze le mélange au moyen d'azote pendant une heure. On chasse le solvant sous vide et on récupère 160 g d'un résidu visqueux.150 g of the above acid (ie 0.33 mole) and 150 ml of benzene are placed in a reactor. The mixture is cooled to 0.degree. C. and a solution of sulfuryl chloride prepared from 44.27 g of water is added dropwise with stirring.
SO 2 Cl 2 (ie 0.33 mole) and 50 ml of benzene so as to maintain the temperature between 0 and 50 ° C. When the casting is complete, the temperature is allowed to rise gradually and then the mixture is degassed with nitrogen for one hour. The solvent is removed in vacuo and 160 g of a viscous residue are recovered.
Rendement : environ 100 %.Yield: about 100%.
d) Préparation de l'acide bis-(dibutoxy-1,3- propyl-2) phosphorique
On met 160 g du chlorure ci-dessus (soit 0,33 mole) et 150 ml d'eau dans le réacteur (mélange non homogène). On refroidit entre 0 et 50C et on coule goutte à goutte 165 ml de soude 4N (soit 0,66 mole). La réaction n'est pas exothermique et on observe la formation du sel de sodium qui est insoluble. La coulée terminée, on laisse sous agitation à température ambiante pendant 1 heure, puis on chauffe à 40-500C pendant une heure. Après refroidissement, on déplace l'acide de son sel de sodium par un acide fort (par exemple HCl). 160 g of the above chloride (ie 0.33 mole) and 150 ml of water are placed in the reactor (non-homogeneous mixture). It is cooled to between 0 ° and 50 ° C. and 165 ml of 4N sodium hydroxide solution (ie 0.66 mol) are added dropwise. The reaction is not exothermic and the formation of the sodium salt which is insoluble is observed. The casting is complete, the mixture is left stirring at room temperature for 1 hour and then heated at 40-500C for one hour. After cooling, the acid is displaced from its sodium salt by a strong acid (for example HCl).
On récupère 140 g de produit. Rendement : 88 %.140 g of product are recovered. Yield: 88%.
Caractérisation du produit : - Dosage de la pureté par potentiométrie
- mono-acide : 97,72 %
- di-acide : 2,52 % - I.R. : # (P=O) = 1235 cm 1 - RMN'H : Confirmation de la structure.
- mono-acid: 97.72%
- di-acid: 2.52% - IR: # (P = O) = 1235 cm 1 - NMR'H: Confirmation of the structure.
<tb><Tb>
Groupement <SEP> CH3- <SEP> -CH2- <SEP> C-CH2 <SEP> C-CH <SEP> CH
<tb> # <SEP> (en <SEP> ppm) <SEP> 0,93 <SEP> 1,47 <SEP> 3,56 <SEP> 4,51 <SEP> 10,81
<tb> Intensité <SEP> 12 <SEP> 16 <SEP> 16 <SEP> 2 <SEP> 1
<tb> Multiplicité <SEP> Triplet <SEP> massif <SEP> massif <SEP> massif <SEP> singulet
<tb> - Analyse élémentaire
<tb>#<SEP> (in <SEP> ppm) <SEP> 0.93 <SEP> 1.47 <SEP> 3.56 <SEP> 4.51 <SEP> 10.81
<tb> Intensity <SEP> 12 <SEP> 16 <SEP> 16 <SEP> 2 <SEP> 1
<tb> Multiplicity <SEP> Triplet <SEP> massive <SEP> massive <SEP> massive <SEP> singlet
<tb> - Elemental Analysis
<tb> C22H47O8P <SEP> Calculé <SEP> Trouvé
<tb> C <SEP> % <SEP> 56,15 <SEP> 54,30 <SEP> - <SEP> 54,11
<tb> <SEP> H <SEP> % <SEP> 10,07 <SEP> 10,21 <SEP> - <SEP> 10,04
<tb>
EXEMPLE 2
Acides mono- et bis- (dipropoxy-1,3-propyl-2) phosphoriques
(R = n C3H7)
a) Préparation du dipropoxy-1,3-propan01-2
<tb> C <SEP>% <SEP> 56.15 <SEP> 54.30 <SEP> - <SEP> 54.11
<tb><SEP> H <SEP>% <SEP> 10.07 <SEP> 10.21 <SEP> - <SEP> 10.04
<Tb>
EXAMPLE 2
Mono- and bis (1,3-dipropoxy-2-propyl) phosphoric acids
(R = n C3H7)
a) Preparation of dipropoxy-1,3-propan01-2
On dissout à chaud 91 g de soude en pastilles à 90 % (soit 2,05 moles) dans 21 moles de propanol anhydre. 91 g of sodium hydroxide in 90% pellets (ie 2.05 moles) are dissolved in hot in 21 moles of anhydrous propanol.
Lorsque la soude est entièrement solubilisée, on laisse refroidir et, à température ambiante, on coule 129 g de dichloro-1,3-propanol-2 (soit 1 mole). La coulée terminée, on chauffe 1 heure au reflux. On observe la formation du précipité de chlorure de sodium. On laisse refroidir, on filtre et on chasse l'excès de propanol. On lave le résidu deux fois à peau. On extrait à l'éther, on sèche sur sulfate de magnésium et on chasse l'éther. On distille le résidu. When the sodium hydroxide is completely solubilized, it is allowed to cool and, at ambient temperature, 129 g of 1,3-dichloro-2-propanol (ie 1 mole) are cast. The casting is complete, it is heated for 1 hour at reflux. The formation of the sodium chloride precipitate is observed. Allowed to cool, filtered and excess propanol removed. The residue is washed twice with skin. It is extracted with ether, dried over magnesium sulphate and the ether is removed. The residue is distilled.
Point d'ébullition : 96-100 C/15 mm Hg. On récupère 105 g de produit. Rendement : environ 60 %. Boiling point: 96-100 ° C./15 mm Hg. 105 g of product are recovered. Yield: about 60%.
b) Préparation des acides bis- et mono-(dipro poxy-1,3-propyl-2) phosphoriques par estérification de l'oxychlorure de phosphore
On met dans un réacteur, 0,6 mole d'alcool (105 g), 0,6 mole de pyridine (soit 47 g) et 150 ml de benzène sec. On admet un courant d'argon et on refroidit entre 0 et +50C. On coule 0,25 mole de POC13 (soit 37 g) dans 50 ml de benzène de façon à maintenir la température audessous de 100C. La coulée terminée, on agite deux heures en laissant revenir à la température ambiante et on laisse au repos pendant 16 heures. 0.6 mol of alcohol (105 g), 0.6 mol of pyridine (ie 47 g) and 150 ml of dry benzene are placed in a reactor. A stream of argon is allowed and cooled between 0 and + 50C. 0.25 mole of POC13 (37 g) is poured into 50 ml of benzene to maintain the temperature below 100C. The casting is complete, the mixture is stirred for two hours and allowed to come to room temperature and is left standing for 16 hours.
c) Hydrolyse et purification
On agite le milieu provenant du stade (b) avec 150 ml d'acide chlorhydrique 2N peudant 5 minutes ; on sépare la couche acide puis on lave la phase organique deux fois au moyen de 250 ml d'acide chlorhydrique N. On agite 3 minutes à chaque fois. On décante la. phase aqueuse. On agite la phase organique avec 60 ml d'acide chlorhydrique 3N dans un Becher avec agitation électromagnétique à une température de 900C pendant 3 heures. Le benzène est évaporé pendant cette opération et on détruit complètement toutes les liaisons P-Cl et la majeure partie des liaisons P-O-P-pyrophosphates. On laisse refroidir et on décante la phase acide. On transvase la phase organique dans un ballon et on élimine l'alcool et l'eau par distillation sous vide à 0,05 mm Hg (la température du bain étant maintenue à 60-650C).La distillation terminée, on chauffe au reflux la phase organique visqueuse avec 60 ml de HCl 3N pendant 48 heures de façon à compléter la destruction des ponts P-O-P. The medium from stage (b) is stirred with 150 ml of 2N hydrochloric acid for 5 minutes; the acidic layer is separated and the organic phase is then washed twice with 250 ml of N hydrochloric acid. The mixture is stirred for 3 minutes each time. We decant the. aqueous phase. The organic phase is stirred with 60 ml of 3N hydrochloric acid in a beaker with electromagnetic stirring at a temperature of 900 ° C. for 3 hours. The benzene is evaporated during this operation and all the P-Cl bonds and most of the P-O-P-pyrophosphate bonds are completely destroyed. The acid phase is allowed to cool and decanted. The organic phase is transferred to a flask and the alcohol and water are distilled off in vacuo at 0.05 mm Hg (the bath temperature is maintained at 60-650 ° C.). viscous organic phase with 60 ml of 3N HCl for 48 hours to complete the destruction of the POP bridges.
On laisse refroidir, on décante la couche aqueuse acide puis on ajoute 300 ml d'heptane. On agite énergiquement pendant 3 minutes puis on extrait la couche organique au moyen de neuf portions de 60 ml d'éthylèneglycol en laissant en contact environ 3 minutes à chaque fois. Le glycol extrait le dérivé mono formé. The mixture is allowed to cool, the acidic aqueous layer is decanted and then 300 ml of heptane are added. The mixture is shaken vigorously for 3 minutes and then the organic layer is extracted with nine 60 ml portions of ethylene glycol leaving in contact for about 3 minutes each time. The glycol extracts the mono derivative formed.
On décante le glycol puis on lave la solution d'heptane trois fois au moyen de 150 ml d'eau distillée. On sèche la phase organique puis on chasse le solvant. On récupère ainsi l'acide bis- (dipropoxy-1,3-propyl-2) phosphorique qui a pu se former. The glycol is decanted and then the heptane solution is washed three times with 150 ml of distilled water. The organic phase is dried and the solvent is removed. The bis (1,3-dipropoxy-2-propyl) phosphoric acid which may have formed is thus recovered.
Caractérisation - Dosage potentiométrique : 1 seule acidité - pureté 98 % - Dosage volumétrique à la soude (phénolphtaléine) - pureté 96,5 % - RMN du proton : conforme à la formule.
<tb><Tb>
<SEP> I <SEP> i <SEP> t <SEP> t <SEP> i
<tb> Groupement <SEP> CH3 <SEP> CH2 <SEP> CH2O <SEP> CHO
<tb> # <SEP> (ppm) <SEP> 0,77 <SEP> 1,44 <SEP> 3,31 <SEP> 4,24
<tb> intensité <SEP> 12 <SEP> 8 <SEP> 16 <SEP> 2
<tb> multiplicité <SEP> triplet <SEP> multiplet <SEP> multiplet <SEP> multiple
<tb>
On dispose ainsi d'un moyen aisé d'isoler les acides désirés de leur milieu dans le cas où ce dernier consisterait en un mélange dans lequel ces acides se trouvent en quantité non négligeable.<SEP> I <SEP> i <SEP> t <SEP> t <SEP> i
<tb> Group <SEP> CH3 <SEP> CH2 <SEP> CH2O <SEP> CHO
<tb>#<SEP> (ppm) <SEP> 0.77 <SEP> 1.44 <SEP> 3.31 <SEP> 4.24
<tb> intensity <SEP> 12 <SEP> 8 <SEP> 16 <SEP> 2
<tb> multiplicity <SEP> triplet <SEP> multiplet <SEP> multiplet <SEP> multiple
<Tb>
There is thus an easy way to isolate the desired acids from their medium in the case where the latter consists of a mixture in which these acids are found in a significant amount.
EXEMPLE 3
Acides mono- et bis-di- (éthyl-2-hexyloxy)-1,3-propyl-2-phos- phorigues
Mono- and bis-di- (2-ethylhexyloxy) -1,3-propyl-2-phosphoric acids
<tb> <SEP> QH
<tb> <SEP> M
<tb> <SEP> (ROCH2)2CHOPi <SEP> (mono)
<tb> (RoCH2)2CHOi21PçOH <SEP> (bis) <SEP> ou
<tb>
R = éthyl-2-hexyle
<tb><SEP> M
<tb><SEP> (ROCH2) 2CHOPi <SEP> (mono)
<tb> (RoCH2) 2CHOi21PçOH <SEP> (bis) <SEP> or
<Tb>
R = 2-ethylhexyl
a) Préparation du dialcoxy-alcool secondaire di-(éthyl-2-hexyloxy)-13-propanol-2
On dissout à chaud 33 g de soude en pastilles à 90 % (0,743 mole) dans 975 g (7,5 moles) d'éthyl-2-hexanol. 33 g of sodium hydroxide in 90% pellets (0.743 mol) are dissolved in hot in 975 g (7.5 moles) of ethyl-2-hexanol.
On laisse refroidir et on coule à température ambiante 46,44 g (0,36 mole) de dichloro-1,3-propanol. On chauffe à 1000C pendant 1 heure. On laisse refroidir, on filtre pour éliminer NaCl et on chasse l'excès d'alcool sous vide. On lave le résidu deux fois à l'eau. On extrait l'éther, on sèche sur sulfate de magnésium et on chasse l'éther. On récupère 100 g de produit (dialcoxy-alcool) (1).46.44 g (0.36 mole) of 1,3-dichloropropanol are allowed to cool and poured at room temperature. It is heated at 1000C for 1 hour. It is allowed to cool, filtered to remove NaCl and the excess alcohol removed under vacuum. The residue is washed twice with water. The ether is extracted, dried over magnesium sulphate and the ether is removed. 100 g of product (dialkoxy alcohol) (1) are recovered.
b) Préparation des acides bis- et mono-phosphouriques
On place 100 g du produit (1) ci-dessus dans un réacteur et on ajoute progressivement à l'abri de l'humidité, 15 g d'anhydride phosphorique. La réaction est exothermique (la température s'élève jusqu'à 350C).b) Preparation of bis- and mono-phosphouric acids
100 g of the product (1) above are placed in a reactor and 15 g of phosphoric anhydride are gradually added in the absence of moisture. The reaction is exothermic (the temperature rises to 350C).
On agite ensuite pendant 3 heures à la température ambiante. Le mélange obtenu est coloré et il peut être décoloré par quelques gouttes d'eau oxygénée. On extrait ensuite le mélange par un solvant organique, on sèche et on chasse le solvant. Lorsque le solvant est le benzène, on obtient un mélange contenant 59,5 % de mono-acide et 33,3 % de diacide, soit près de 2/3 de mono-acide. It is then stirred for 3 hours at room temperature. The mixture obtained is colored and it can be discolored by a few drops of hydrogen peroxide. The mixture is then extracted with an organic solvent, dried and the solvent removed. When the solvent is benzene, there is obtained a mixture containing 59.5% of mono-acid and 33.3% of diacid, or nearly 2/3 of mono-acid.
Il va du reste de soi que la présente invention n'a été décrite qu'à titre purement explicatif et nullement limitatif et que toute modification utile pourra y être apportée sans sortir de son cadre tel que défini par les revendications ci-après. It goes without saying that the present invention has been described only as a purely explanatory and non-limiting and that any useful modification can be made without departing from its scope as defined by the claims below.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8017877A FR2492826B1 (en) | 1980-08-13 | 1980-08-13 | MONO- AND BIS- (DIALCOXY-1,3-PROPYL-2) PHOSPHORIC ACIDS AND MINERAL SALTS AND THE PROCESS FOR OBTAINING THEM |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8017877A FR2492826B1 (en) | 1980-08-13 | 1980-08-13 | MONO- AND BIS- (DIALCOXY-1,3-PROPYL-2) PHOSPHORIC ACIDS AND MINERAL SALTS AND THE PROCESS FOR OBTAINING THEM |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2492826A1 true FR2492826A1 (en) | 1982-04-30 |
| FR2492826B1 FR2492826B1 (en) | 1984-10-05 |
Family
ID=9245173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8017877A Expired FR2492826B1 (en) | 1980-08-13 | 1980-08-13 | MONO- AND BIS- (DIALCOXY-1,3-PROPYL-2) PHOSPHORIC ACIDS AND MINERAL SALTS AND THE PROCESS FOR OBTAINING THEM |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2492826B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115845758A (en) * | 2021-09-24 | 2023-03-28 | 浙江医药股份有限公司新昌制药厂 | Continuous reaction device and method for preparing phosphoric acid diester compound through continuous reaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3445547A (en) * | 1964-12-01 | 1969-05-20 | Hooker Chemical Corp | Preparation of esters of phosphoric acid |
| US4205022A (en) * | 1978-09-05 | 1980-05-27 | Velsicol Chemical Corporation | 2,2-Bis(haloalkyl)-3-hydroxy-1-propyl phosphoric acids |
-
1980
- 1980-08-13 FR FR8017877A patent/FR2492826B1/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3445547A (en) * | 1964-12-01 | 1969-05-20 | Hooker Chemical Corp | Preparation of esters of phosphoric acid |
| US4205022A (en) * | 1978-09-05 | 1980-05-27 | Velsicol Chemical Corporation | 2,2-Bis(haloalkyl)-3-hydroxy-1-propyl phosphoric acids |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115845758A (en) * | 2021-09-24 | 2023-03-28 | 浙江医药股份有限公司新昌制药厂 | Continuous reaction device and method for preparing phosphoric acid diester compound through continuous reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2492826B1 (en) | 1984-10-05 |
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