WO2006108585A1 - Reaction products of phosphonoesters with alcohols or amines - Google Patents
Reaction products of phosphonoesters with alcohols or amines Download PDFInfo
- Publication number
- WO2006108585A1 WO2006108585A1 PCT/EP2006/003231 EP2006003231W WO2006108585A1 WO 2006108585 A1 WO2006108585 A1 WO 2006108585A1 EP 2006003231 W EP2006003231 W EP 2006003231W WO 2006108585 A1 WO2006108585 A1 WO 2006108585A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- reaction
- phosphorus compounds
- radical
- alcohols
- Prior art date
Links
- 150000001298 alcohols Chemical class 0.000 title claims abstract description 25
- 150000001412 amines Chemical class 0.000 title claims abstract description 22
- 239000007795 chemical reaction product Substances 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 150000003018 phosphorus compounds Chemical class 0.000 claims abstract description 23
- 108090000790 Enzymes Proteins 0.000 claims abstract description 16
- 102000004190 Enzymes Human genes 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- -1 hydridosiloxanes Chemical class 0.000 claims abstract description 15
- 210000002268 wool Anatomy 0.000 claims abstract description 12
- 239000001913 cellulose Substances 0.000 claims abstract description 8
- 229920002678 cellulose Polymers 0.000 claims abstract description 8
- 150000003254 radicals Chemical class 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 23
- 108090000787 Subtilisin Proteins 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 6
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 4
- 229930024421 Adenine Natural products 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229960000643 adenine Drugs 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 5
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 abstract description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001733 carboxylic acid esters Chemical group 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 22
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 13
- 239000004753 textile Substances 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 230000004913 activation Effects 0.000 description 7
- 238000001994 activation Methods 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- FBELJLCOAHMRJK-UHFFFAOYSA-L disodium;2,2-bis(2-ethylhexyl)-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCC(CC)CC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CC(CC)CCCC FBELJLCOAHMRJK-UHFFFAOYSA-L 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical class [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- KMDMOMDSEVTJTI-UHFFFAOYSA-N 2-phosphonobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)P(O)(O)=O KMDMOMDSEVTJTI-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 3
- 239000008363 phosphate buffer Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000007342 radical addition reaction Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- ABIFUJNCKIMWRZ-JGVFFNPUSA-N (2r,4s)-4-(3-phosphonopropyl)piperidine-2-carboxylic acid Chemical compound OC(=O)[C@H]1C[C@@H](CCCP(O)(O)=O)CCN1 ABIFUJNCKIMWRZ-JGVFFNPUSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 101150041968 CDC13 gene Proteins 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 108010056079 Subtilisins Proteins 0.000 description 2
- 102000005158 Subtilisins Human genes 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000009988 textile finishing Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- REIOYEWGAMBNBT-UHFFFAOYSA-N (1,4-dimethoxy-1,4-dioxobutan-2-yl)phosphonic acid Chemical compound COC(=O)CC(P(O)(O)=O)C(=O)OC REIOYEWGAMBNBT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 108090000604 Hydrolases Proteins 0.000 description 1
- 102000004157 Hydrolases Human genes 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 108010022999 Serine Proteases Proteins 0.000 description 1
- 102000012479 Serine Proteases Human genes 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 108060008539 Transglutaminase Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- STYUEUAAPQZSTL-UHFFFAOYSA-N methyl 2-dimethoxyphosphorylpropanoate Chemical group COC(=O)C(C)P(=O)(OC)OC STYUEUAAPQZSTL-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- FMNMEQSRDWIBFO-UHFFFAOYSA-N propanoyl phosphate Chemical compound CCC(=O)OP(O)(O)=O FMNMEQSRDWIBFO-UHFFFAOYSA-N 0.000 description 1
- OZEUWRHVPSZFQI-UHFFFAOYSA-N propyl 2-dimethoxyphosphorylpropanoate Chemical group COP(=O)(OC)C(C(=O)OCCC)C OZEUWRHVPSZFQI-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 102000003601 transglutaminase Human genes 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C07F9/28—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
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
Definitions
- This invention relates to phosphorus compounds preparable from certain phosphonoesters by reaction with certain alcohols or amines. This invention further relates to phosphorus compounds obtainable therefrom by further chemical reactions with specific products or by addition polymerization.
- Esters of phosphono carboxylic acids are known and widely used.
- One example of a use is the flameproofing sector where N-methyloldialkylphosphonopropionamide is utilized as a flame retardant for cellulosic textiles.
- M represents a divalent saturated, linear or branched alkyiene radical having 1 to 4 carbon atoms, preferably -CH 2 -CH 2 - or -CH 2 -CH(CH 3 )-, where X represents H or
- CH 2 C(R 4 )-CH 2 - but not more than one of the R 3 radicals represents H, where R 4 represents H or CH 3 .
- the specified phosphorus compounds of the present invention have various possible uses, although any one particular use may depend on their specific chemical structure, in particular on the identity of the R 2 and R 3 radicals.
- the products obtained in the reaction of the esters of the formula (I) or the formula (II) with alcohols or amines are further reacted, this further reaction being either a) a reaction with a poiyorganosiloxane containing Si-H bonds, or b) a free radical polymerization, or a reaction with celiuiose molecules, or a reaction with wool materials, or a reaction with an alcohol of the formula (V)
- R 5 is a monovalent heterocyclic radical containing one or more nitrogen atoms and T represents a linear or branched, saturated or unsaturated divalent hydrocarbyl radical having 1 to 4 carbon atoms.
- the products formed in the reaction of compounds of the formula (I) and/or of the formula (II) with compounds of the formula (III) in each of which R 2 is an unsaturated radical are very useful for preparing polymers.
- the monomers or oligomers present on the fabric can subsequently, if desired, be polymerized with the assistance of a known free radical initiator.
- a further interesting possibility of using the products which are formed after the reaction with unsaturated alcohols, for example with (meth)allyl alcohol consists in reacting them with polyorganosiloxanes ("H-siloxanes") which contain Si-H bonds. In this reaction, Si-H bonds add onto carbon-carbon double bonds.
- H-siloxanes polyorganosiloxanes
- the products thus obtained can in turn be used for the treatment of fibrous materials, for example textile fabrics in the form of wovens, knits or nonwovens. They can here in turn act as polymeric flame retardants and, as the case may be, additionally confer a soft hand.
- products according to the present invention are used for the treatment of fibrous materials, especially textile fabrics, they can be used in the form of aqueous solutions or dispersions for this purpose. But they can also be used in the form of solutions in organic solvents, for example N,N-dialkylformamide.
- Dispersants useful for preparing aqueous dispersions are known to one skilled in the art. Such dispersants include commercially available surface-active products such as ethoxylated alcohols, ethoxylated fatty acids, ethoxylated fatty amines and quaternary ammonium salts.
- the application of the products - A - to textile fabrics can be effected in accordance with generally known methods in the course of textile finishing or enhancement, by padding for example.
- the aqueous solutions or dispersions used for this purpose may also include further products known to one skilled in the art of textile finishing. Examples are soft hand agents and oil- and/or water-repellent agents.
- Products in accordance with the present invention (or aqueous dispersions or solutions or solutions in organic solvents thereof) which are formed after the reaction of phosphonoesters of the formula (I) and/or of the formula (II) with alcohols of the formula (III) are very useful for application to textile fabrics comprising cellulose, for example cotton articles. It may also be possible if appropriate to use a commercially available compound of the formula (I) or of the formula (II) directly for application to textiles, but it is often advantageous to replace the R 1 radical in commercially available phosphorus compounds of the formula (I) or of the formula (II) by an R 2 radical and this can be done by reaction (transesterification) with an alcohol of the formula (III).
- the phosphorus compounds in accordance with the present invention are useful for treating cellulosic, cotton or wool woven fabrics. It is possible here to catalyze the formation of a chemical bond between the fabric and the phosphorus compound by means of an enzyme, for example by means of a lipase, a subtilisin or by means of transglutaminases. For example, an aqueous microemulsion of enzyme, phosphate buffer and surfactant can be applied to the fabric, the fabric subsequently dried and then the phosphorus compound applied from water or organic solvent.
- the wool materials are preferably textile fabrics, for example wovens.
- the reaction is preferably carried out with products preparable from phosphonoesters of the formula (I) and/or of the formula (II) by reaction with amines of the formula (IV).
- the wool textiles can in turn be advantageous or necessary for the wool textiles to be heated during or after application of the products and/or the reaction to be catalyzed.
- the products can be applied to textile articles composed of wool by methods known for wool finishing.
- R 5 is a monovalent heterocyclic radical containing one or more nitrogen atoms as ring atoms and
- T represents a linear or branched, saturated or unsaturated divalent hydrocarbyl radical having 1 to 4 carbon atoms.
- R 5 radical in the formula (V) is a monovalent radical derived from adenine (1 H ⁇ purine-6-amine) by removal of the hydrogen atom on the amino group of the 5 ring.
- Modified adenines are obtainable through the above-described reaction with compounds of the formula (V). It is well known that physiological effects are obtainable with adenine (derivatives).
- Phosphorus compounds in accordance with the present invention are obtainable by reaction of phosphonoesters of the formula (I) or of the formula (II)
- phosphorus compounds in accordance with the present invention can be prepared as mentioned by reacting the products obtained in the stated reaction with polysiloxanes containing Si-H bonds or with cellulose molecules or with wool materials or with alcohols of the formula (V) or subjecting them to a free radical addition polymerization.
- the phosphonoesters of the formula (I) that are useful as starting materials are preparable by known methods.
- One possibility is to add dialkyl phosphites onto ⁇ , ⁇ -unsaturated carboxylic esters having 3 or 4 carbon atoms in the acid component.
- Acrylic or methacrylic esters are particularly suitable. Such addition reactions are described in the above-cited US patents.
- a number of phosphonoesters of the formula (II) can be prepared in accordance with the teaching of US 2 754 319 when X represents a hydrogen atom.
- Il P(OR) 2 and z is 0 are obtainable by reaction of 2-butyn-1 ,4-dicarboxylic esters with dialkyl phosphite.
- a number of phosphorus compounds in accordance with the present invention are preparable by reacting phosphonoesters of the formula (I) or of the formula (II) or a mixture of phosphonoesters of the formula (I) and of the formula (II) with alcohols of the formula R 2 -OH or a mixture of such alcohols.
- the stated mixture of phosphonoesters can be a mixture including only two or more compounds of the formula (I) or a mixture including only two or more compounds of the formula (II). But it can also be a mixture including not only one or more compounds of the formula (I) and additionally one or more compounds of the formula (II).
- the suitable alcohols of the formula (III), namely alcohols of the formula R 2 -OH are mono- or polyhydric alcohols which can be saturated or unsaturated, linear or branched and contain 2 to
- polyvinyl alcohols examples are polyvinyl alcohols.
- examples of such alcohols are ethylene glycol, propylene glycol, glycerol and also monohydric alcohols having 2 to 6 carbon atoms, examples being propanol or butanol.
- AIIyI alcohol or methallyl alcohol are very particularly useful alcohols of the formula (III). Their reaction with the stated phosphono compounds gives rise, through transesterification, to esters containing olefinic double bonds and therefore accessible to further chemical reactions such as, for example, a free radical addition polymerization or a reaction. with polysiloxanes containing Si-H bonds.
- phosphorus compounds in accordance with the present invention are obtainable by reaction of phosphonoesters of the formula (I) or of the formula (II) or the abovementioned mixtures of such compounds with amines of the formula (IV), i.e., amines of the formula (R 3 ) 2 NH, or mixtures of such amines.
- the two R 3 radicals must not both be hydrogen.
- the starting compounds be used in such amounts that the sum total of the -OH groups in the compounds of the formula (III) or the sum total of the amino groups, i.e., the -NH groups, in the compounds of the formula (IV) is equal to the sum total of the OR 1 radicals in the compounds of the formula (I) and of the formula (II) used.
- the aforementioned reactions of the phosphonoesters with alcohols or amines can be performed by methods that are common knowledge in organic chemistry. These reactions have the -OR 1 radicals of the phosphonoesters replaced by -OR 2 or -N(R 3 ) 2 radicals. It is advantageous and in some cases even necessary for a catalyst to be used in the reaction. Suitable catalysts are known from the chemical literature. They include dilute mineral acids. Useful catalysts further include alkali metal hydroxides and alkali metal carbonates or mixtures thereof. It is also possible to use acidic potassium orthophosphates or triethylamine.
- the reaction of the phosphonoesters with R 2 -OH alcohols or (R 3 ) 2 NH amines can also be effectively catalyzed by means of suitable enzymes.
- Enzymatic catalysis has the advantage over conventional catalysis by means of organic or inorganic compounds, in a number of cases, that the enzyme-catalyzed reaction can take place at a lower temperature, i.e., under gentler conditions, and more selectively, i.e., with the formation of a smaller amount of by-products.
- Useful catalysts include hydrolytic enzymes such as serine-proteases or hydrolases or proteases ("R ⁇ mpp, Chemie-Lexikon".
- E.G. 3.4.21.62 is the so-called EC No., a classification number for enzymes, see R ⁇ mpp- Kompakt, Lexikon Biochemie und Molekularbioloqie, page 151 , Georg Thieme publishers,
- Subtilisin Carisberg is available from Novozymes of Denmark under the designation "Alcalase
- Subtilisin Carisberg E. C. 3.4.21.62 is first activated. Without activation, no reaction.
- Activation can be effected by means of potassium salts or sodium salts such as sodium acetate, sodium sulfate, sodium fluoride, potassium acetate, potassium sulfate or potassium fluoride (see Ru et al., 2000, On the salt-induced activation of lyophilized enzymes in organic solvents: effect of salz kosmotropicity on on enzyme activity, J. Am Chem. Soc, 122, 1565-1571). The use of sodium acetate is preferable.
- Activation can also be effected by means of an anionic surfactant such as sodium dioctyl sulfosuccinate. Possible forms of the two activations are described hereinbelow.
- the two solutions are intensively commixed in a homogenizer (Ultra-Turrax T25, IKA- Labortechnik, Staufen) at 15 000 rpm and O 0 C for 5 minutes.
- a homogenizer Ultra-Turrax T25, IKA- Labortechnik, Staufen
- the stable, milkily cloudy emulsion is subsequently freeze dried.
- the enzyme catalyzing the reaction is preferably used in amounts ranging from 10 to 150 mg of pure enzyme per 100 mmol/l of substrate.
- Enzyme-catalyzed activated subtilisin as enzyme reaction of a phosphonoester of the formula (I) with alcohol or amine
- Example 2a was repeated except that 1 -propylamine was used in place of 1-propanol and the incubation time was only 2 days.
- PPME methyl dimethylphosphonopropionate (starting compound)
- PPPE 1 -propyl dimethylphosphonopropionate
- Control blank test carried out under the same reaction conditions, including incubation, but without addition of enzyme
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Abstract
Phosphono compounds containing carboxylic ester groups are reacted with alcohols or amines. This reaction can be catalyzed by means of chemical compounds or by means of enzymes. The phosphorus compounds obtained are useful, depending on their structure, for preparing polymers, for reaction with hydridosiloxanes, for binding to cellulose or wool or for manufacturing products having flame-retardant properties.
Description
Reaction products of phosphonoesters with alcohols or amines
This invention relates to phosphorus compounds preparable from certain phosphonoesters by reaction with certain alcohols or amines. This invention further relates to phosphorus compounds obtainable therefrom by further chemical reactions with specific products or by addition polymerization.
Esters of phosphono carboxylic acids are known and widely used. One example of a use is the flameproofing sector where N-methyloldialkylphosphonopropionamide is utilized as a flame retardant for cellulosic textiles.
There is still a need, however, to expand the existing range of phosphono compounds in order thereby to open up novel possible uses.
It is an object of the present invention to provide novel phosphorus compounds that are useful for various purposes, for example for preparing polymeric phosphono compounds or for reaction with polyhydridoorganosiloxanes or for attachment to articles composed of natural polymers such as cellulosic or wool materials.
We have found that this object is achieved by phosphorus compounds preparable by reaction of phosphonoesters of the formula (I) or of the formula (II) or of a mixture of phosphonoesters of the formula (I) and of the formula (II)
O O
Il Il 1
(RO)2 P-M-C- OR m
(RO)2
with alcohols of the formula (III) or amines of the formula (IV) or a mixture of alcohols of the formula (III) or of a mixture of amines of the formula (IV)
R2-0H (III)
(R3)2NH (iV)
where M represents a divalent saturated, linear or branched alkyiene radical having 1 to 4 carbon atoms, preferably -CH2-CH2- or -CH2-CH(CH3)-, where X represents H or
O Il P(OR)2 where z is 0 or 1 and Y represents an M radical or an M radical in which one hydrogen is replaced by a
O Il -P(OR)2 radical, where all the R radicals present independently represent an alkyl group having 1 to 4 carbon atoms, preferably -CH3, all R1 radicals present independently represent -CH3 or -CH2-CH3, where R2-OH is a mono- or polyhydric saturated or unsaturated alcohol having 2 to 6 carbon atoms or polyvinyl alcohol, all the R3 radicals present represent R or H or
CH2=C(R4)-CH2- but not more than one of the R3 radicals represents H, where R4 represents H or CH3.
The specified phosphorus compounds of the present invention have various possible uses, although any one particular use may depend on their specific chemical structure, in particular on the identity of the R2 and R3 radicals.
In a preferred embodiment of phosphorus compounds of the present invention the products obtained in the reaction of the esters of the formula (I) or the formula (II) with alcohols or amines
are further reacted, this further reaction being either a) a reaction with a poiyorganosiloxane containing Si-H bonds, or b) a free radical polymerization, or a reaction with celiuiose molecules, or a reaction with wool materials, or a reaction with an alcohol of the formula (V)
R5-T-OH (V)
where R5 is a monovalent heterocyclic radical containing one or more nitrogen atoms and T represents a linear or branched, saturated or unsaturated divalent hydrocarbyl radical having 1 to 4 carbon atoms.
For example, the products formed in the reaction of compounds of the formula (I) and/or of the formula (II) with compounds of the formula (III) in each of which R2 is an unsaturated radical are very useful for preparing polymers. A preferred example thereof is products formed by reaction of the phosphono compounds of the formula (I) and/or formula (11) with (meth)allyl alcohol. These products still contain C=C double bonds, which permit a free radical addition polymerization. Owing to the presence of phosphorus, the products obtained after addition polymerization can serve as polymeric flame retardants, for example as flame retardants for textiles. It is convenient here to apply the products obtained after reaction with (meth)allyl alcohol to a textile fabric, for example a woven fabric, before polymerization has taken place. The monomers or oligomers present on the fabric can subsequently, if desired, be polymerized with the assistance of a known free radical initiator. A further interesting possibility of using the products which are formed after the reaction with unsaturated alcohols, for example with (meth)allyl alcohol, consists in reacting them with polyorganosiloxanes ("H-siloxanes") which contain Si-H bonds. In this reaction, Si-H bonds add onto carbon-carbon double bonds. The products thus obtained can in turn be used for the treatment of fibrous materials, for example textile fabrics in the form of wovens, knits or nonwovens. They can here in turn act as polymeric flame retardants and, as the case may be, additionally confer a soft hand.
When products according to the present invention, or converted products thereof, are used for the treatment of fibrous materials, especially textile fabrics, they can be used in the form of aqueous solutions or dispersions for this purpose. But they can also be used in the form of solutions in organic solvents, for example N,N-dialkylformamide. Dispersants useful for preparing aqueous dispersions are known to one skilled in the art. Such dispersants include commercially available surface-active products such as ethoxylated alcohols, ethoxylated fatty acids, ethoxylated fatty amines and quaternary ammonium salts. The application of the products
- A - to textile fabrics can be effected in accordance with generally known methods in the course of textile finishing or enhancement, by padding for example. The aqueous solutions or dispersions used for this purpose may also include further products known to one skilled in the art of textile finishing. Examples are soft hand agents and oil- and/or water-repellent agents.
Products in accordance with the present invention (or aqueous dispersions or solutions or solutions in organic solvents thereof) which are formed after the reaction of phosphonoesters of the formula (I) and/or of the formula (II) with alcohols of the formula (III) are very useful for application to textile fabrics comprising cellulose, for example cotton articles. It may also be possible if appropriate to use a commercially available compound of the formula (I) or of the formula (II) directly for application to textiles, but it is often advantageous to replace the R1 radical in commercially available phosphorus compounds of the formula (I) or of the formula (II) by an R2 radical and this can be done by reaction (transesterification) with an alcohol of the formula (III).
The phosphorus compounds in accordance with the present invention are useful for treating cellulosic, cotton or wool woven fabrics. It is possible here to catalyze the formation of a chemical bond between the fabric and the phosphorus compound by means of an enzyme, for example by means of a lipase, a subtilisin or by means of transglutaminases. For example, an aqueous microemulsion of enzyme, phosphate buffer and surfactant can be applied to the fabric, the fabric subsequently dried and then the phosphorus compound applied from water or organic solvent.
A number of compounds of the formula (I) can be prepared by the known addition of dialkyl phosphite onto (meth)acrylic esters CH2=CH-COOR1 or CH2=C(CH3)-COOR1. Suitable methods and processing conditions for this purpose are described in US 2 754 320 and US 2 971 019. Since esters of the formula (I) are commercially available as starting compounds only with certain R1 radicals, it can be advantageous in a number of cases for the R1 radical to be replaced by an R2 radical by reaction (transesterification) with an R2-OH alcohol. R2 radicals other than R1 can then if appropriate offer advantages with regard to the finishing of cellulosic textiles, for example in relation to the durability of the finishing effects. After the specified products have been applied to cellulose materials, chemical bonding of the products to cellulose can be effected by chemical reaction (transesterification) with the cellulose's hydroxyl groups. This bestows good durability to the conferred properties. The chemical reaction between the identified products and cellulose molecules is if appropriate initiated or favored by elevated temperature. But in any case it is of advantage to facilitate the reaction by use of a catalyst or of a mixture of catalysts. Suitable catalysts are known to one skilled in the art, namely customary esterification/transesterification catalysts such as dilute acids. Further suitable catalysts are mentioned hereinbelow. They include enzymes.
A further possible use for products of the present invention is the reaction with wool materials. The resulting products are likewise products that are in accordance with the present invention. The wool materials are preferably textile fabrics, for example wovens. The reaction is preferably carried out with products preparable from phosphonoesters of the formula (I) and/or of the formula (II) by reaction with amines of the formula (IV). To form a chemical bond between these phosphorus compounds and the fabrics composed of wool, it can in turn be advantageous or necessary for the wool textiles to be heated during or after application of the products and/or the reaction to be catalyzed. As for the rest, the products can be applied to textile articles composed of wool by methods known for wool finishing.
In a further preferred embodiment of phosphorus compounds that are in accordance with the present invention, first a reaction of phosphonoesters of the formula (I) and/or of the formula (II) with one or more alcohols of the formula (III) is carried out and the product obtained is reacted with an alcohol of the formula (V)
R5-T-OH (V)
where
R5 is a monovalent heterocyclic radical containing one or more nitrogen atoms as ring atoms and
T represents a linear or branched, saturated or unsaturated divalent hydrocarbyl radical having 1 to 4 carbon atoms.
In a preferred embodiment the R5 radical in the formula (V) is a monovalent radical derived from adenine (1 H~purine-6-amine) by removal of the hydrogen atom on the amino group of the 5 ring.
Modified adenines are obtainable through the above-described reaction with compounds of the formula (V). It is well known that physiological effects are obtainable with adenine (derivatives).
Phosphorus compounds in accordance with the present invention are obtainable by reaction of phosphonoesters of the formula (I) or of the formula (II)
O I O
I l I
1
(RO)2 P-M- C-OR
0)
- 6 - or of mixtures comprising a plurality of esters of the formula (I) and/or of the formula (II) with alcohols of the formula (III) or amines of the formula (IV)
R2-0H (III)
(R3) 2NH ' (IV)
or with a mixture of alcohols of the formula (III) or of a mixture of amines of the formula (IV).
Further phosphorus compounds in accordance with the present invention can be prepared as mentioned by reacting the products obtained in the stated reaction with polysiloxanes containing Si-H bonds or with cellulose molecules or with wool materials or with alcohols of the formula (V) or subjecting them to a free radical addition polymerization.
The phosphonoesters of the formula (I) that are useful as starting materials are preparable by known methods. One possibility is to add dialkyl phosphites onto α,β-unsaturated carboxylic esters having 3 or 4 carbon atoms in the acid component. Acrylic or methacrylic esters are particularly suitable. Such addition reactions are described in the above-cited US patents.
A number of phosphonoesters of the formula (II) can be prepared in accordance with the teaching of US 2 754 319 when X represents a hydrogen atom.
Esters of the formula (II) where X represents
O
Il P(OR)2 and z is 0 are obtainable by reaction of 2-butyn-1 ,4-dicarboxylic esters with dialkyl phosphite. An addition of the P-H bond of the phosphite onto the C≡C triple bond takes place in a first step to form modified maleic esters or fumaric esters in each of which one of the carbon atoms of the C=C double bond has a phosphono group attached to it. In a second step, a further P-H bond of a second phosphite molecule is added onto the resulting C=C double bond to obtain compounds of the formula (II) where X =
O
Il P(OR)2
A number of phosphorus compounds in accordance with the present invention are preparable by reacting phosphonoesters of the formula (I) or of the formula (II) or a mixture of phosphonoesters of the formula (I) and of the formula (II) with alcohols of the formula R2-OH or a mixture of such alcohols. The stated mixture of phosphonoesters can be a mixture including only two or more compounds of the formula (I) or a mixture including only two or more compounds of the formula (II). But it can also be a mixture including not only one or more compounds of the formula (I) and additionally one or more compounds of the formula (II). The suitable alcohols of the formula (III), namely alcohols of the formula R2-OH, are mono- or
polyhydric alcohols which can be saturated or unsaturated, linear or branched and contain 2 to
6 carbon atoms, or are polyvinyl alcohols. Examples of such alcohols are ethylene glycol, propylene glycol, glycerol and also monohydric alcohols having 2 to 6 carbon atoms, examples being propanol or butanol. AIIyI alcohol or methallyl alcohol are very particularly useful alcohols of the formula (III). Their reaction with the stated phosphono compounds gives rise, through transesterification, to esters containing olefinic double bonds and therefore accessible to further chemical reactions such as, for example, a free radical addition polymerization or a reaction. with polysiloxanes containing Si-H bonds.
Other phosphorus compounds in accordance with the present invention are obtainable by reaction of phosphonoesters of the formula (I) or of the formula (II) or the abovementioned mixtures of such compounds with amines of the formula (IV), i.e., amines of the formula (R3)2NH, or mixtures of such amines. Here R3 represents hydrogen or an R radical, i.e., an alkyl group having 1 to 4 carbon atoms, or an allyl or methallyl group CH2=CH-CH2- or CH2=C(CH3)-CH2-. However, the two R3 radicals must not both be hydrogen.
With regard to the reaction of the phosphonoesters of the formula (I) or of the formula (II) or of mixtures of such esters with alcohols R2-OH or amines (R3)2NH, it is preferred that the starting compounds be used in such amounts that the sum total of the -OH groups in the compounds of the formula (III) or the sum total of the amino groups, i.e., the -NH groups, in the compounds of the formula (IV) is equal to the sum total of the OR1 radicals in the compounds of the formula (I) and of the formula (II) used.
The aforementioned reactions of the phosphonoesters with alcohols or amines can be performed by methods that are common knowledge in organic chemistry. These reactions have the -OR1 radicals of the phosphonoesters replaced by -OR2 or -N(R3)2 radicals. It is advantageous and in some cases even necessary for a catalyst to be used in the reaction. Suitable catalysts are known from the chemical literature. They include dilute mineral acids. Useful catalysts further include alkali metal hydroxides and alkali metal carbonates or mixtures thereof. It is also possible to use acidic potassium orthophosphates or triethylamine.
The reaction of the phosphonoesters with R2-OH alcohols or (R3)2NH amines can also be effectively catalyzed by means of suitable enzymes. Enzymatic catalysis has the advantage over conventional catalysis by means of organic or inorganic compounds, in a number of cases, that the enzyme-catalyzed reaction can take place at a lower temperature, i.e., under gentler conditions, and more selectively, i.e., with the formation of a smaller amount of by-products. Useful catalysts include hydrolytic enzymes such as serine-proteases or hydrolases or proteases ("Rδmpp, Chemie-Lexikon". 9th edition, 1992, page 4362, Georg Thieme publishers, Stuttgart - New York). In almost anhydrous organic solvents such as benzene or toluene for
example, these enzymes are capable of catalyzing the reverse reaction to hydrolysis, for example the synthesis of esters and amides. Subtilisins such as "Subtilisin Carisberg" (E. C.
3.4.21.62) will be found particularly useful for this reaction.
E.G. 3.4.21.62 is the so-called EC No., a classification number for enzymes, see Rδmpp- Kompakt, Lexikon Biochemie und Molekularbioloqie, page 151 , Georg Thieme publishers,
Stuttgart - New York, 2000.
Subtilisin Carisberg is available from Novozymes of Denmark under the designation "Alcalase
1.5 MG1 Type FG".
To synthesize esters and amides in organic solvents, Subtilisin Carisberg E. C. 3.4.21.62 is first activated. Without activation, no reaction. Activation can be effected by means of potassium salts or sodium salts such as sodium acetate, sodium sulfate, sodium fluoride, potassium acetate, potassium sulfate or potassium fluoride (see Ru et al., 2000, On the salt-induced activation of lyophilized enzymes in organic solvents: effect of salz kosmotropicity on on enzyme activity, J. Am Chem. Soc, 122, 1565-1571). The use of sodium acetate is preferable. Activation can also be effected by means of an anionic surfactant such as sodium dioctyl sulfosuccinate. Possible forms of the two activations are described hereinbelow.
Salt activation of subtilisin:
1 g of Subtilisin Carisberg E.G. 3.4.21.62 is dissolved in 200 ml of 2.87 mM (pH = 7.8) phosphate buffer with 0.66 mol I"1 sodium acetate x 3H2O and freeze dried. Activation of subtilisin by means of sodium bis(2-ethylhexyl) sulfosuccinate (SBSE) 1 g of Subtilisin Carisberg E. C. 3.4.21.62 is dissolved in 20 ml of phosphate buffer of a concentration of 2.87 mmol I"1 (pH = 7.8). 100 mmol I"1 of SBSE are dissolved in 20 ml of toluene. The two solutions are intensively commixed in a homogenizer (Ultra-Turrax T25, IKA- Labortechnik, Staufen) at 15 000 rpm and O0C for 5 minutes. The stable, milkily cloudy emulsion is subsequently freeze dried.
The enzyme catalyzing the reaction is preferably used in amounts ranging from 10 to 150 mg of pure enzyme per 100 mmol/l of substrate.
The invention will now be illustrated by operative examples.
Example 1
A mixture of
1 g of (CH3O)2P(O)CH2CH2COOCH3
(= phosphonoester of the formula (I) where R = CH3, R1 = CH3, M = -CH2-CH2-)
20 g of allyl alcohol
0.8 g of sodium carbonate were mixed together, and the mixture was heated to 8O0C. The
sodium carbonate acted as a catalyst.
The mixture was maintained at 800C with stirring for 6 hours. During this period, excess allyl alcohol was continuously distilled off at reduced pressure. Then, the mixture was cooled down to room temperature, a further 20 g of allyl alcohol were added and the mixture was stirred for another 8 hours. The product obtained was filtered and excess allyl alcohol was removed in a rotary evaporator. The resulting allyl ester (CH3O)2P(O)CH2CH2COOCH2 CH=CH2 was of high purity (gas chromatography).
Example 2
Enzyme-catalyzed (activated subtilisin as enzyme) reaction of a phosphonoester of the formula (I) with alcohol or amine
2a) Reaction with alcohol
A solution of 100 mmol/l of phosphonoester of the formula (I) where R = R1=CH3, M = -CH2-CH2- and 850 mmol/l of 1-propanol in 5 ml of anhydrous benzene was prepared. To this solution were added 1 g.of molecular sieves (4 A, from Merck) and activated Subtilisin
Carlsberg E.C. 3.4.21.62, specifically in one run 1.9 g of the abovementioned sodium acetate activated subtilisin, in another run 0.19 g of the above-described SBSE-activated subtilisin. In either case, the amount of pure subtilisin added was 0.1 g. The two suspensions obtained were incubated in sealed vessels on a shaking machine
(70 rpm) at 37°C for 7 days.
2b) Reaction with amine
Example 2a) was repeated except that 1 -propylamine was used in place of 1-propanol and the incubation time was only 2 days.
The products obtained in accordance with Examples 2a and 2b were subsequently analyzed by gas chromatography (Chrompack model 438 A, CP-Sil-8 CB capillary column, injection, detector and column temperatures 25O0C, 2800C and 15O0C respectively). Tables 1 and 2 hereinbelow show the results, table 1 relating to the reaction with 1-propanol and table 2 to the reaction with 1 -propylamine. The numbers in the tables are mol %.
Key to other abbreviations in the table:
PPME = methyl dimethylphosphonopropionate (starting compound)
PPPE = 1 -propyl dimethylphosphonopropionate
(= reaction product of Example 2a)
PPPA = N-1-propyldimethylphosphonopropioπamide
(= reaction product of Example 2b)
Control = blank test carried out under the same reaction conditions, including incubation, but without addition of enzyme
Table 1 (to Example 2a)
Table 2 (to Example 2b)
It is observed that a small amount of PPME has converted to PPPE and to PPPA (3.7 and 2.4 mol% respectively) after incubation even without addition of enzyme ("control" columns). However, in the experiments with added subtilisin, the yields of the respective reaction products were distinctly higher than in the case of the control experiments. The SBSE-activated subtilisin had a more favorable effect on the reaction with propyl alcohol than on that with propylamine. By contrast, the subtilisin activated with sodium acetate had a more favorable effect on the reaction with propylamine than on that with propanol.
Examples 3 and 4
Example 3
Transesterification of trimethyl phosphonopropionate, catalyzed by potassium phosphate
350 g of (CH3O)2P(O)CH2CH2COOCH3 are mixed with 350 ml of allyl alcohol and 61 g of potassium phosphate are added. The mixture is heated to 80°C and a reduced pressure of 750 - 800 mbar is applied. A further 2 I of allyl alcohol are added dropwise within 2 days and at the same time the same amount is distilled off together with methanol. After 2 days, the catalyst is filtered off and the reaction mixture is concentrated in a rotary evaporator to leave 386 g of a pale yellow oil.
300 MHz 1H NMR (CDC13 = 7.26 ppm): 5.84 (1 H, ddt), 5.25 (1 H, dd), 5.16 (1 H, dd), 4.51 (1H, dd), 3.68 (3H, s), 3.63 (3H, s), 2.55 (2H, m), 2.03 (2H, m). 150 MHz 13C NMR: 171.4, 132.0, 118.4, 65.6, 52.7, 52.6, 27.4, 21.1 , 19.2. 121 MHz P31 NMR: 33.25
Example 4
Transesterification of tetramethyi phosphonosuccinate, catalyzed by anhydrous sodium carbonate
700 g of tetramethyi phosphonosuccinate (= phosphonoester as per formula Il of claim 1 where z = 0, R = CH3, R1 = CH3, X = P(O)(OCH3)2) are dissolved in 1.65 I of allyl alcohol and admixed with 78.4 g of (anhydrous) sodium carbonate. The reaction mixture is heated to 50 - 70°C under reduced pressure, the reduced pressure setting being such that methanol being released is ■ continuously distilled off. Fresh allyl alcohol is continuously added. After about 2 days, the catalyst is filtered off. Distillative removal of the solvent in a rotary evaporator leaves a mixture composed of about 80% of bisallyl dimethyl phosphonosuccinate and monoallyl trimethyl phosphonosuccinate (starting material).
300 MHz 1H NMR (CDC13 = 7.26 ppm): 5.86 (2H, m), 5.34 (2H, m), 5.21 (2H, m), 4.60 (4H, m), 3.78 (3H, d), 3.74 (3H, d), 3.50 (2H1 m), 3.07 (2H, m), 2.83 (2H, m). 150 MHz 13C NMR: 170.6, 167.8, 131.9, 131.6, 118.8, 118.7, 66.7, 66.0, 53.8, 53.7, 41.9, 40.1 , 31.7. 121 MHz P31 NMR: 24.25
Claims
1. Phosphorus compounds preparable by reaction of phosphonoesters of the formula (I) or of the formula (II) or of a mixture of phosphonoesters of the formula (I) and of the formula (II)
O O
Il
(RO)2 P-M-C-OR
(O
(RO)2
with alcohols of the formula (III) or amines of the formula (IV) or a mixture of alcohols of the formula (III) or of a mixture of amines of the formula (IV)
R2-OH (III)
(R3)2NH (IV)
where M represents a divalent saturated, linear or branched alkylene radical having 1 to 4 carbon atoms, preferably -CH2-CH2- or -CH2-CH(CH3)-, where X represents H or
P(OR)2 where z is O or 1 and Y represents an M radical or an M radical in which one hydrogen is replaced by a
O
Il -P(OR)2 radical, where all the R radicals present independently represent an alkyl group having 1 to 4 carbon atoms, preferably -CH3, all R1 radicals present independently represent -CH3 Or -CH2-CH3, where R2-OH is a mono- or polyhydric saturated or unsaturated alcohol having 2 to 6 carbon atoms or polyvinyl alcohol, all the R3 radicals present represent R or H or CH2=C(R4)-CH2~ but not more than one of the R3 radicals represents H, where R4 represents H or CH3.
2. The phosphorus compounds according to claim 1 wherein R2-OH is ailyl alcohol or methallyl alcohol.
3. The phosphorus compounds according to claim 1 or 2 wherein the starting compounds are used in such amounts that the sum total of the -OH groups in the compounds of the formula (III) or the sum total of the amino groups in the compounds of the formula (IV) is equal to the sum total of the OR1 radicals in the compounds of the formula (I) and of the formula (II) used.
4. The phosphorus compounds according to one or more of claims 1 to 3 wherefor a catalyst is used in the reaction.
5. The phosphorus compounds according to claim 4 wherefor an enzyme is used as catalyst.
6. The phosphorus compounds according to claim 5 wherein a subtilisin is used as catalyst.
7. The phosphorus compounds according to claim 4 wherefor an alkali metal hydroxide or an alkali metal carbonate or a mixture thereof is used as catalyst.
8. The phosphorus compounds according to one or more of claims 1 to 7 wherefor the products obtained in the reaction of the esters of the formula (I) or the formula (II) with alcohols or amines are further reacted, this further reaction being either a) a reaction with a polyorganosiloxane containing Si-H bonds, or b) a free radical polymerization, or a reaction with cellulose molecules, or a reaction with wool materials, or a reaction with an alcohol of the formula (V)
R5-T-OH (V)
where R5 is a monovalent heterocyclic radical containing one or more nitrogen atoms and T represents a linear or branched, saturated or unsaturated divalent hydrocarbyl radical having 1 to 4 carbon atoms.
9. The phosphorus compounds according to claim 8 wherein R5 is a monovalent radical derived from adenine (1 H-purine-6-amine) by removal of the hydrogen atom on the amino group of the 5 ring.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05008018A EP1719795A1 (en) | 2005-04-13 | 2005-04-13 | Reaction products of phosphonoesters with alcohols or amines |
| EP05008018.3 | 2005-04-13 |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2754319A (en) * | 1948-07-01 | 1956-07-10 | Union Carbide & Carbon Corp | Production of diesterified phosphono derivatives of polyfunctional organic compounds |
| US2754320A (en) * | 1948-06-24 | 1956-07-10 | Union Carbide & Carbon Corp | Production of diesterified phosphono derivatives of monofunctional compounds |
| US2875232A (en) * | 1956-02-14 | 1959-02-24 | Eastman Kodak Co | Phosphonoalkanamides prepared from phosphites and lactams |
| US2971019A (en) * | 1948-07-10 | 1961-02-07 | Us Rubber Co | Organo-phosphorus compounds |
| US3196190A (en) * | 1959-07-17 | 1965-07-20 | Bayer Ag | Flame-resistant polyester resinous compositions containing halogen and phosphorus |
| US3361784A (en) * | 1963-10-30 | 1968-01-02 | Shell Oil Co | Polymer stabilization |
| US3423369A (en) * | 1966-01-14 | 1969-01-21 | Ciba Ltd | Phosphorus-containing aminoplasts and process for their preparation |
| US4254018A (en) * | 1977-03-01 | 1981-03-03 | Akzona Incorporated | Linear polyesters containing phosphonate heat stabilizers |
| WO1994021724A1 (en) * | 1993-03-23 | 1994-09-29 | Courtaulds Plc | Phosphorus-containing flame retardants |
| US5648509A (en) * | 1994-07-29 | 1997-07-15 | Ciba-Geigy Corporation | Process for the preparation of diesters of phosphonocarboxylic acid derivatives |
-
2005
- 2005-04-13 EP EP05008018A patent/EP1719795A1/en not_active Withdrawn
-
2006
- 2006-04-08 WO PCT/EP2006/003231 patent/WO2006108585A1/en not_active Application Discontinuation
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2754320A (en) * | 1948-06-24 | 1956-07-10 | Union Carbide & Carbon Corp | Production of diesterified phosphono derivatives of monofunctional compounds |
| US2754319A (en) * | 1948-07-01 | 1956-07-10 | Union Carbide & Carbon Corp | Production of diesterified phosphono derivatives of polyfunctional organic compounds |
| US2971019A (en) * | 1948-07-10 | 1961-02-07 | Us Rubber Co | Organo-phosphorus compounds |
| US2875232A (en) * | 1956-02-14 | 1959-02-24 | Eastman Kodak Co | Phosphonoalkanamides prepared from phosphites and lactams |
| US3196190A (en) * | 1959-07-17 | 1965-07-20 | Bayer Ag | Flame-resistant polyester resinous compositions containing halogen and phosphorus |
| US3361784A (en) * | 1963-10-30 | 1968-01-02 | Shell Oil Co | Polymer stabilization |
| US3423369A (en) * | 1966-01-14 | 1969-01-21 | Ciba Ltd | Phosphorus-containing aminoplasts and process for their preparation |
| US4254018A (en) * | 1977-03-01 | 1981-03-03 | Akzona Incorporated | Linear polyesters containing phosphonate heat stabilizers |
| WO1994021724A1 (en) * | 1993-03-23 | 1994-09-29 | Courtaulds Plc | Phosphorus-containing flame retardants |
| US5648509A (en) * | 1994-07-29 | 1997-07-15 | Ciba-Geigy Corporation | Process for the preparation of diesters of phosphonocarboxylic acid derivatives |
Non-Patent Citations (3)
| Title |
|---|
| DATABASE CROSSFIRE BEILSTEIN Beilstein Institut, Frankfurt am Main, De; 21 January 2004 (2004-01-21), XP002335502 * |
| LÀSZLO T.: "A Versatile Building Block for Synthesis of Substituted Cyclopropanephosphonic Acid Esters", TETRAHEDRON, vol. 51, no. 33, 1995, pages 9167 - 9178, XP002335500 * |
| MOO JE SUNG: "Synthetic Studies towords Sarain A", J. ORG. CHEM., vol. 68, no. 6, 2003, pages 2205 - 2208 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1719795A1 (en) | 2006-11-08 |
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