US2900408A - Acid esters of acyl-phosphorous acids and method of making the same - Google Patents
Acid esters of acyl-phosphorous acids and method of making the same Download PDFInfo
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- US2900408A US2900408A US657496A US65749657A US2900408A US 2900408 A US2900408 A US 2900408A US 657496 A US657496 A US 657496A US 65749657 A US65749657 A US 65749657A US 2900408 A US2900408 A US 2900408A
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- United States
- Prior art keywords
- acid
- phosphorous
- acyl
- phosphite
- acid esters
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- 239000002253 acid Substances 0.000 title claims description 28
- 150000002148 esters Chemical class 0.000 title description 22
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- -1 di-substituted phosphites Chemical class 0.000 description 42
- 239000000203 mixture Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 9
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 9
- 229960003750 ethyl chloride Drugs 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WQCRMVOOMCEJJY-UHFFFAOYSA-N C(CCCCCCCCCCC)(=O)P(O)(O)O Chemical compound C(CCCCCCCCCCC)(=O)P(O)(O)O WQCRMVOOMCEJJY-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 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 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- PSFDQSOCUJVVGF-UHFFFAOYSA-N harman Chemical compound C12=CC=CC=C2NC2=C1C=CN=C2C PSFDQSOCUJVVGF-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-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
- YZBOVSFWWNVKRJ-UHFFFAOYSA-M 2-butoxycarbonylbenzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1C([O-])=O YZBOVSFWWNVKRJ-UHFFFAOYSA-M 0.000 description 1
- WFSGQBNCVASPMW-UHFFFAOYSA-N 2-ethylhexanoyl chloride Chemical compound CCCCC(CC)C(Cl)=O WFSGQBNCVASPMW-UHFFFAOYSA-N 0.000 description 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- HCEBNYOSBIWVJS-UHFFFAOYSA-N C(C)(=O)P(O)(O)O Chemical compound C(C)(=O)P(O)(O)O HCEBNYOSBIWVJS-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PHTGBYLTEVVMMK-UHFFFAOYSA-N [P]C(=O)c1ccccc1 Chemical compound [P]C(=O)c1ccccc1 PHTGBYLTEVVMMK-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- LSNGYVCUKHMBSY-UHFFFAOYSA-N phosphono dodecanoate Chemical compound CCCCCCCCCCCC(=O)OP(O)(O)=O LSNGYVCUKHMBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 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
- C07F9/4062—Esters of acids containing the structure -C(=X)-P(=X)(XR)2 or NC-P(=X)(XR)2, (X = O, S, Se)
- C07F9/4065—Esters of acids containing the structure -C(=X)-P(=X)(XR)2, (X = O, S, Se)
Definitions
- This invention relates to acid esters of acyl-phosphorous acids and their salts and to a method of preparing the same from halides of monobasic or polybasic carboxylic acids and di-substituted phosphites.
- the ethyl ester of acetyl-phosphorous acid or benZoyl-phosphorous acid may be obtained by a reaction between acetyl chloride or benzoyl chloride and triethyl phosphite.
- the neutral esters thus obtained decompose upon saponification either into the corresponding carboxylic acid and phosphorous acid or into the corresponding aldehyde and phosphoric acid. It is therefore not possible to produce acid esters of acyl-phosphorous acids or their salts by this method.
- acid esters of acyl-phosphorous acids may be produced in a very simple fashion by reacting halides of monobasic or polybasic carboxylic acids with di-substituted phosphites at elevated temate peratures.
- a monocarboxylic acid halide is used,
- reaction in accordance with the present invention probablyproceeds in accordance with the following general equation.
- R and R represent identical or dilierent aliphatic or cycloaliphatic hydrocarbon radicals with preferably less than 8 carbon atoms
- R" represents an aliphatic, cycloaliphatic or aromatic hydrocarbon radical.
- the radicals R, R and R" may be straight-chain hydrocarbon radicals or also branched-chain hydrocarbon radicals. They may also be substituted, for example halogensubstituted.
- the radical R may 'in addition be interrupted by heteroatoms; that is, by oxygen, sulfur or nitrogen atoms. If the halide of a dibasic or polybasic carboxylic acid is used as the starting material for the process in accordance with the invention, dibasic or polybasic acid esters are formed in analogous fashion, for example, in accordance with the following equation:
- the halides preferably the chlorides or bromides, of aliphatic, cycloaliphatic or aromatic monocarboxylic, dicarboxylic or polycarboxylic acids, the hydrocarbon radicals of which carry various substit-uents or t 2 are also interrupted by heteroatoms or hetero atom groups, may be used as starting materials for the process according to the present invention; such acids are, for example, acetic acid, butyric acid, isobutyric acid, lauric acid and higher fatty acids, mono-, di-jand trichloroacetic acid, as well as other halogenated carboxylic acids, ether-carboxylic acids, thioether-carboxylic acids, aminocarboxylic acids, cyclohexane-carboxylic acid, benzoic acid and other substituted or unsubstituted.
- acids are, for example, acetic acid, butyric acid, isobutyric acid, lauric acid and higher fatty acids, mono-, di
- aromatic carboxylic acids as Well as diand poly-carboxylic acids, such as adipic acid, sebacic acid, tricarballylic acid, phthalic acid, tetrachlorophthalic acid, terephthalic acid, trlmesic acid, and the like.
- Di substituted phosphites which may be reacted with the carboxylic acid halides in accordance with the invention are, for example, diethyl phosphite, di-isopropyl phosphite, dibutyl phosphite, dioctyl phosphite, di-(Z- chloroethyD-phosphite, and the like.
- the two reaction components are preferably used in quantitative ratios such that about one mol of di-substituted phosphite is present for each CO-Hal group.
- the reaction takes place at elevated temperatures, preferably between 50 and C.
- elevated temperatures preferably between 50 and C.
- an inert organic solvent or diluent such as carbon tetrachlorodie or benzene.
- the reaction proceeds with the formation of an aliphatic or cycloaliphatic halide. If a low-molecular aliphatic alcohol is used for the production of the disubstituted phosphite, this hydrocarbon halide continuously distills out of the reaction mixture during the reaction. If a high-molecular aliphatic or cycloaliphatic alcohol is used to produce disubstituted phosphite, the hydrocarbon halide may be distilled off vacuo during or after the reaction.
- the acid esters of acyl-phosphorous acids obtained by reaction in accordance with the invention are useful as capillary-active agents for various purposes, for example as cleaning agents or washing agents.
- the acid ester of acy-l-phosphorous acid as described above may be transformed into their salts, for example their alkali metal salts in a very simple fashion.
- These salts are likewise useful as capillary-active agents and may be used alone or with usual substances, for example phosphates, alka line carbonates and silicates as washing agents, cleaning agents or as textile-finishing agents.
- the acid esters may also be transformed into other acid esters by ester-radical exchange or into neutral esters by heating them, preferably with high-molecular alcohols and, necessary, in the presence of suitable esterification catalysts.
- polybasic esters of acyl-phosphorous acids produced from the halides of diand polycarboxylic acids in accordance with the present invention may also be reacted with polyvalent alcohols to form acid or also neutral polyesters of varying molecular size.
- Example vI 29.2 gm. of the residue were stirred with a solution of to s. s daei asa a 7 3 4 gm. sodium hydroxide in 1.4 liters water. foaming, turbid solution, similar to a soap solution, was formed. From this solution the pure sodium salt of the monoethyl ester of lauroyl phosphorous acid was obtained in a solid form by salt-ing out with sodium chloride.
- Example II A mixture of 61 gm. adipic acid dichloride and 92 gm. diethyl-phosphite was stirred for 8 hours at 90-95 C.; 40 gm. ethyl chloride distilled ofi during that time. The reaction product, the di-monoethyl ester of adipoyl phosphorous acid, was a colorless, viscous: liquid which dissolved in water to form a clear solution having an acid reaction.
- Example III A mixture of 55.2 gm. diethyl-phosphite and 56.2 gm. benzoyl chloride was heated for 20 hours at a temperature between 85 and 95 C., accompanied by stirring; 25 gm.
- Example IV A mixture of 19 gm. capric acid chloride and 14.5 gm. diethyl-phosphite was stirred for 8 hours at a temperature between 85 and 95 C.; 6 gm. ethyl chloride distilled'off during that time. The residue, the monoethyl ester of caproyl phosphorous acid, was a clear, colorless, moderately viscous oil which was readily soluble in dilute sodium hydroxide.
- Example V A mixture of 81, gm. 2-ethylhexanoic acid chloride and 69 gm. diethyl phosphite was stirred for about6 hours at a temperature between 90 and 95 C. until no more ethyl chloride distilled oflf. 102 gm. of the moderately viscous residue formed thereby were heated in admixture with 112 gm. Z-ethylhexanol at 100 C. while passing a slow stream of nitrogen therethrough until a reduction in weight of 17 gm. occurred. Thereafter, the excess Z-ethylhexanol was distilled oil at a vacuum of 2.5 mm. Hg.
- the residue had an acid number of 142 and a saponification value of 273 (calculated values for C7H15cO-PO(OH)OC3H17Z143 and 286, respectively).
- the acid ester dissolved in dilute sodium hydroxide. The solution foamed and exhibited excellent wetting properties.
- Example VI A mixture of 109.3 gm. lauroyl chloride and 97 gm. dibutyl phosphite was heated to 95 C. while passing nitrogen therethrough; the butyl chloride formed thereby was trapped in a condenser. After about 20 hours no more butyl chloride split E. The reduction in weight of the reaction mixture was 43.5 gm. The residue was a viscous, almost colorless oil. The phosphorus and carbon content of the reaction product corresponded to the formula The chlorine content was smaller than 0.1%. The acid number was 182l86 (calculated 175) and the saponification value was 355-363 (calculated 350).
- Example VII For the cleaning of foodstuff containers, preferably of metal there is excellently suited a product of the following composition: V V 30% by weight trisodium phosphate (12 H 0).
- Example VIII 50 parts trisodium phosphate 20 parts sodium tripolyphosphate 10 parts sodium sulfate 20 parts acid ester, obtained as described in Example I, paragraph 1 are mixed. The product obtained in this manner after dissolving in water (about 10 grams per liter) is an excellent dishwashing composition.
- Example IX A cleaning agent of similar quality is obtained, if in the above (Example VIII) indicated combination, the acid ester is replaced by 20 parts of the sodium salt of the acid ester, which is described inExample I, paragraph 2.
- Example X An excellent metal cleaning agent is obtained by preparing a 2% aqueous solution of a mixture of the fol lowing composition:
- Example II obtained as described in Example II 50 parts sodium sulfate 24 parts sodium pyrophosphate (Na H P O 1 part 2-mercaptobenzthiazol.
- the process of producing acid esters of acyl-phosphorous acid which comprises heating a mixture of an organic carboxylic acid halide and a di-lower alkyl phosphite in a ratio of 1 mol di-lower alkyl phosphite per -CO-halide group in the carboxylic acid halide to a temperature between 50 and 150 C., and removing the lower alkyl halide from the reaction mixture.
- the process of producing the monoethyl ester of caproyl phosphorous acid which comprises heating a mixture of equimolar amounts of capn'c acid chloride and diethyl-phosphite to a temperature between 85 and 95 C., and removing the ethyl chloride formed thereby from the reaction mixture.
- the process of producing the monoethyl ester of Z-ethylhexanoyl phosphorous acid which comprises heating a mixture of equimolar amounts of Z-ethylhexanoic acid chloride and diethyl-phosphite to a temperature between 90 and 95 C., and removing the ethyl chloride formed thereby from the reaction mixture.
- R is an alkyl radical
- R" is selected from the group consisting of monoand di-valent saturated aliphatic and aromatic hydrocarbon radicals containing 1 to 7 carbon atoms and the radicals of saturated monovalent higher fatty acids, and the alkali metal salts thereof.
- Acid esters of acyl-phosphorous acids having a structural formula selected from the group consisting of and A OR
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEH26995A DE1010965B (de) | 1956-05-08 | 1956-05-08 | Verfahren zur Herstellung von sauren Estern der Acylphosphonsaeuren bzw. ihrer Salze |
Publications (1)
Publication Number | Publication Date |
---|---|
US2900408A true US2900408A (en) | 1959-08-18 |
Family
ID=7150451
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US657496A Expired - Lifetime US2900408A (en) | 1956-05-08 | 1957-05-07 | Acid esters of acyl-phosphorous acids and method of making the same |
Country Status (3)
Country | Link |
---|---|
US (1) | US2900408A (de) |
DE (1) | DE1010965B (de) |
GB (1) | GB810642A (de) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3012054A (en) * | 1960-03-18 | 1961-12-05 | Dow Chemical Co | Tetraalkyl esters of diphosphonates |
US3118876A (en) * | 1958-07-26 | 1964-01-21 | Takeda Pharmaceutical | Process for preparing glycoside phosphates |
US3214454A (en) * | 1958-09-06 | 1965-10-26 | Henkel & Compagnie G M B H | Process of forming metal ion complexes |
US3324202A (en) * | 1963-07-09 | 1967-06-06 | Fmc Corp | Phosphorus-containing polyols |
US3378610A (en) * | 1964-11-18 | 1968-04-16 | Chemagro Corp | Phenoxyacetyl phosphonates |
US3400148A (en) * | 1965-09-23 | 1968-09-03 | Procter & Gamble | Phosphonate compounds |
US3676532A (en) * | 1969-11-21 | 1972-07-11 | Olin Corp | Alpha-(dialkoxyphosphinyl)aryl methyl dialkyl phosphates |
US3899496A (en) * | 1970-10-06 | 1975-08-12 | Henkel & Cie Gmbh | Production of 1-aminoalkane-1,1-diphosphonic acids |
US3940436A (en) * | 1970-04-13 | 1976-02-24 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
US3944599A (en) * | 1970-04-13 | 1976-03-16 | Monsanto Company | Substituted ethane diphosphonic acids and salts |
US3957858A (en) * | 1970-04-13 | 1976-05-18 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
US4339443A (en) * | 1978-09-22 | 1982-07-13 | Fbc Limited | Compounds and compositions |
US4348332A (en) * | 1980-10-23 | 1982-09-07 | Bayer Aktiengesellschaft | Phosphonoformaldehyde, a process for its preparation and its use as an intermediate product for the preparation of medicaments |
US4911887A (en) * | 1988-11-09 | 1990-03-27 | W. R. Grace & Co.-Conn. | Phosphonic acid compounds and the preparation and use thereof |
US4981648A (en) * | 1988-11-09 | 1991-01-01 | W. R. Grace & Co.-Conn. | Inhibiting corrosion in aqueous systems |
US5017306A (en) * | 1988-11-09 | 1991-05-21 | W. R. Grace & Co.-Conn. | Corrosion inhibitor |
US5266722A (en) * | 1988-11-09 | 1993-11-30 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US5410060A (en) * | 1992-12-05 | 1995-04-25 | Basf Aktiengesellschaft | Process for preparation of arenebisphosphine oxides |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL132418C (de) * | 1962-04-13 | |||
DE2965566D1 (en) * | 1978-07-14 | 1983-07-07 | Basf Ag | Acylphosphinoxide compounds, their preparation and their use |
FR2489711A1 (fr) * | 1980-04-21 | 1982-03-12 | Minemet Rech Sa | Compositions echangeuses de cations metalliques |
IL91362A0 (en) * | 1989-08-20 | 1990-03-19 | Yissum Res Dev Co | Bisphosphonates,process for preparing them and pharmaceutical compositions containing them |
US5196409A (en) * | 1989-08-20 | 1993-03-23 | Yissum, Research Development Company Of The Hebrew University Of Jerusalem | Bisphosphonates, pharmaceutical compositions, and process for the treatment of irregularities in calcium metabolism |
DE4033215A1 (de) * | 1990-10-19 | 1992-04-23 | Hoechst Ag | Acyl-(2'-hydroxybiphenyl-2-yl)-phosphinsaeuresalze, ihre herstellung und verwendung |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2491920A (en) * | 1946-05-16 | 1949-12-20 | Du Pont | Diesters of 1-ketophosphonic acids |
US2629731A (en) * | 1951-03-07 | 1953-02-24 | Shell Dev | Esters of phosphonoformic acids and polyhydric alcohols |
US2719167A (en) * | 1953-04-13 | 1955-09-27 | Ciba Ltd | Compounds containing phosphorus and process therefor |
-
1956
- 1956-05-08 DE DEH26995A patent/DE1010965B/de active Pending
-
1957
- 1957-05-03 GB GB14121/57A patent/GB810642A/en not_active Expired
- 1957-05-07 US US657496A patent/US2900408A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2491920A (en) * | 1946-05-16 | 1949-12-20 | Du Pont | Diesters of 1-ketophosphonic acids |
US2629731A (en) * | 1951-03-07 | 1953-02-24 | Shell Dev | Esters of phosphonoformic acids and polyhydric alcohols |
US2719167A (en) * | 1953-04-13 | 1955-09-27 | Ciba Ltd | Compounds containing phosphorus and process therefor |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3118876A (en) * | 1958-07-26 | 1964-01-21 | Takeda Pharmaceutical | Process for preparing glycoside phosphates |
US3214454A (en) * | 1958-09-06 | 1965-10-26 | Henkel & Compagnie G M B H | Process of forming metal ion complexes |
US3012054A (en) * | 1960-03-18 | 1961-12-05 | Dow Chemical Co | Tetraalkyl esters of diphosphonates |
US3324202A (en) * | 1963-07-09 | 1967-06-06 | Fmc Corp | Phosphorus-containing polyols |
US3378610A (en) * | 1964-11-18 | 1968-04-16 | Chemagro Corp | Phenoxyacetyl phosphonates |
US3400148A (en) * | 1965-09-23 | 1968-09-03 | Procter & Gamble | Phosphonate compounds |
US3676532A (en) * | 1969-11-21 | 1972-07-11 | Olin Corp | Alpha-(dialkoxyphosphinyl)aryl methyl dialkyl phosphates |
US3940436A (en) * | 1970-04-13 | 1976-02-24 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
US3944599A (en) * | 1970-04-13 | 1976-03-16 | Monsanto Company | Substituted ethane diphosphonic acids and salts |
US3957858A (en) * | 1970-04-13 | 1976-05-18 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
US3899496A (en) * | 1970-10-06 | 1975-08-12 | Henkel & Cie Gmbh | Production of 1-aminoalkane-1,1-diphosphonic acids |
US4339443A (en) * | 1978-09-22 | 1982-07-13 | Fbc Limited | Compounds and compositions |
US4348332A (en) * | 1980-10-23 | 1982-09-07 | Bayer Aktiengesellschaft | Phosphonoformaldehyde, a process for its preparation and its use as an intermediate product for the preparation of medicaments |
US4911887A (en) * | 1988-11-09 | 1990-03-27 | W. R. Grace & Co.-Conn. | Phosphonic acid compounds and the preparation and use thereof |
US4981648A (en) * | 1988-11-09 | 1991-01-01 | W. R. Grace & Co.-Conn. | Inhibiting corrosion in aqueous systems |
US5017306A (en) * | 1988-11-09 | 1991-05-21 | W. R. Grace & Co.-Conn. | Corrosion inhibitor |
US5266722A (en) * | 1988-11-09 | 1993-11-30 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US5312953A (en) * | 1988-11-09 | 1994-05-17 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US5410060A (en) * | 1992-12-05 | 1995-04-25 | Basf Aktiengesellschaft | Process for preparation of arenebisphosphine oxides |
Also Published As
Publication number | Publication date |
---|---|
GB810642A (en) | 1959-03-18 |
DE1010965B (de) | 1957-06-27 |
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