US3299123A - Substituted methylene diphosphonic acids and salts and esters thereof - Google Patents
Substituted methylene diphosphonic acids and salts and esters thereof Download PDFInfo
- Publication number
- US3299123A US3299123A US271607A US27160763A US3299123A US 3299123 A US3299123 A US 3299123A US 271607 A US271607 A US 271607A US 27160763 A US27160763 A US 27160763A US 3299123 A US3299123 A US 3299123A
- Authority
- US
- United States
- Prior art keywords
- ester
- methylene
- esters
- compounds
- diphosphonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000002148 esters Chemical class 0.000 title description 39
- 150000003839 salts Chemical class 0.000 title description 21
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical class OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 30
- -1 hydrogen ions Chemical class 0.000 description 74
- 239000002253 acid Substances 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 28
- 150000007513 acids Chemical class 0.000 description 23
- 229940102859 methylene diphosphonate Drugs 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003599 detergent Substances 0.000 description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 125000002877 alkyl aryl group Chemical group 0.000 description 9
- 125000003710 aryl alkyl group Chemical group 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical class OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- XCXJLWLQQPJVDR-UHFFFAOYSA-N 3-(azepan-2-yl)quinoline Chemical compound C1CCCCNC1C1=CN=C(C=CC=C2)C2=C1 XCXJLWLQQPJVDR-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- HWZUDASOMGNLSM-UHFFFAOYSA-N O=P1OCOP(=O)O1 Chemical compound O=P1OCOP(=O)O1 HWZUDASOMGNLSM-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229940073608 benzyl chloride Drugs 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical class [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 230000003381 solubilizing effect Effects 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005108 dry cleaning Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009919 sequestration Effects 0.000 description 3
- LKGJFSBVIBNBPW-UHFFFAOYSA-N (2-phenyl-1-phosphonoethyl)phosphonic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)CC1=CC=CC=C1 LKGJFSBVIBNBPW-UHFFFAOYSA-N 0.000 description 2
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 2
- URFPRAHGGBYNPW-UHFFFAOYSA-N 1-bromo-4-ethylbenzene Chemical compound CCC1=CC=C(Br)C=C1 URFPRAHGGBYNPW-UHFFFAOYSA-N 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AKCZEKXQVYPQTC-UHFFFAOYSA-N 1,3-xylene;dihydrochloride Chemical compound Cl.Cl.CC1=CC=CC(C)=C1 AKCZEKXQVYPQTC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- LNWXALCHPJANMJ-UHFFFAOYSA-N 1-(bromomethyl)-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(CBr)=C1 LNWXALCHPJANMJ-UHFFFAOYSA-N 0.000 description 1
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- AQLKCZOZKNQXDW-UHFFFAOYSA-N 1-bromo-4-tert-butylcyclohexane Chemical compound CC(C)(C)C1CCC(Br)CC1 AQLKCZOZKNQXDW-UHFFFAOYSA-N 0.000 description 1
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- WSULSMOGMLRGKU-UHFFFAOYSA-N 1-bromooctadecane Chemical compound CCCCCCCCCCCCCCCCCCBr WSULSMOGMLRGKU-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 description 1
- OGYBTPYJHQSBBR-UHFFFAOYSA-N 1-chloro-1-methylcyclohexane Chemical compound CC1(Cl)CCCCC1 OGYBTPYJHQSBBR-UHFFFAOYSA-N 0.000 description 1
- BASMANVIUSSIIM-UHFFFAOYSA-N 1-chloro-2-(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1Cl BASMANVIUSSIIM-UHFFFAOYSA-N 0.000 description 1
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- RNEMUWDQJSRDMQ-UHFFFAOYSA-N 1-chloro-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1Cl RNEMUWDQJSRDMQ-UHFFFAOYSA-N 0.000 description 1
- DDGRAFHHXYIQQR-UHFFFAOYSA-N 1-chloro-3-(chloromethyl)benzene Chemical compound ClCC1=CC=CC(Cl)=C1 DDGRAFHHXYIQQR-UHFFFAOYSA-N 0.000 description 1
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 1
- IIDPVAQJDNIXKZ-UHFFFAOYSA-N 1-chloro-3-methylcyclohexane Chemical compound CC1CCCC(Cl)C1 IIDPVAQJDNIXKZ-UHFFFAOYSA-N 0.000 description 1
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 1
- JOLVAWCDDOEWSH-UHFFFAOYSA-N 1-chloro-4-phenylcyclohexa-2,4-dien-1-amine Chemical group C1=CC(N)(Cl)CC=C1C1=CC=CC=C1 JOLVAWCDDOEWSH-UHFFFAOYSA-N 0.000 description 1
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- ZHKKNUKCXPWZOP-UHFFFAOYSA-N 1-chloroundecane Chemical compound CCCCCCCCCCCCl ZHKKNUKCXPWZOP-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- ROKLPPRTPHAGFK-UHFFFAOYSA-N 1-phosphonooctylphosphonic acid Chemical compound CCCCCCCC(P(O)(O)=O)P(O)(O)=O ROKLPPRTPHAGFK-UHFFFAOYSA-N 0.000 description 1
- MYSJYDYZEABHHG-UHFFFAOYSA-N 1-phosphonotridecylphosphonic acid Chemical compound CCCCCCCCCCCCC(P(O)(O)=O)P(O)(O)=O MYSJYDYZEABHHG-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- ODTQUKVFOLFLIQ-UHFFFAOYSA-N 2-[di(propan-2-yloxy)phosphorylmethyl-propan-2-yloxyphosphoryl]oxypropane Chemical compound CC(C)OP(=O)(OC(C)C)CP(=O)(OC(C)C)OC(C)C ODTQUKVFOLFLIQ-UHFFFAOYSA-N 0.000 description 1
- NCKMMSIFQUPKCK-UHFFFAOYSA-N 2-benzyl-4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1CC1=CC=CC=C1 NCKMMSIFQUPKCK-UHFFFAOYSA-N 0.000 description 1
- LCLLDGIGXHMJPL-UHFFFAOYSA-N 2-bromo-3,4-dinitrothiophene Chemical compound [O-][N+](=O)C1=CSC(Br)=C1[N+]([O-])=O LCLLDGIGXHMJPL-UHFFFAOYSA-N 0.000 description 1
- VWGRESZTMULPDE-UHFFFAOYSA-N 2-bromo-5-methylfuran Chemical compound CC1=CC=C(Br)O1 VWGRESZTMULPDE-UHFFFAOYSA-N 0.000 description 1
- QGTDMAKRJHGXOF-UHFFFAOYSA-N 2-bromo-5-nitrofuran Chemical compound [O-][N+](=O)C1=CC=C(Br)O1 QGTDMAKRJHGXOF-UHFFFAOYSA-N 0.000 description 1
- JFNPFFAEYZRVJS-UHFFFAOYSA-N 2-bromocycloheptan-1-one Chemical compound BrC1CCCCCC1=O JFNPFFAEYZRVJS-UHFFFAOYSA-N 0.000 description 1
- OYMCMWPHMPODNK-UHFFFAOYSA-N 2-bromofuran Chemical compound BrC1=CC=CO1 OYMCMWPHMPODNK-UHFFFAOYSA-N 0.000 description 1
- HZTPKMIMXLTOSK-UHFFFAOYSA-N 2-bromohexanoic acid Chemical compound CCCCC(Br)C(O)=O HZTPKMIMXLTOSK-UHFFFAOYSA-N 0.000 description 1
- IFMWWVGVDOTBNN-UHFFFAOYSA-N 2-chloro-2,3,3-trimethylbutane Chemical compound CC(C)(C)C(C)(C)Cl IFMWWVGVDOTBNN-UHFFFAOYSA-N 0.000 description 1
- HJBUWTLHZIRBIM-UHFFFAOYSA-N 2-chloro-4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C(Cl)=C1 HJBUWTLHZIRBIM-UHFFFAOYSA-N 0.000 description 1
- WLHBVLZZOJGNGQ-UHFFFAOYSA-N 2-chloro-4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C(Cl)=C1 WLHBVLZZOJGNGQ-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- LJEOEPPSGGLCKY-UHFFFAOYSA-N 2-chlorocyclopenta-1,3-diene Chemical compound ClC1=CCC=C1 LJEOEPPSGGLCKY-UHFFFAOYSA-N 0.000 description 1
- IVKPBNVMLKJSFG-UHFFFAOYSA-N 2-chloronaphthalene-1-carbaldehyde Chemical compound C1=CC=CC2=C(C=O)C(Cl)=CC=C21 IVKPBNVMLKJSFG-UHFFFAOYSA-N 0.000 description 1
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 1
- GSFNQBFZFXUTBN-UHFFFAOYSA-N 2-chlorothiophene Chemical compound ClC1=CC=CS1 GSFNQBFZFXUTBN-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- WMPPDTMATNBGJN-UHFFFAOYSA-N 2-phenylethylbromide Chemical compound BrCCC1=CC=CC=C1 WMPPDTMATNBGJN-UHFFFAOYSA-N 0.000 description 1
- UMHAQPJPKHTAHZ-UHFFFAOYSA-N 3,4-dichlorooxolane Chemical compound ClC1COCC1Cl UMHAQPJPKHTAHZ-UHFFFAOYSA-N 0.000 description 1
- AJKDUJRRWLQXHM-UHFFFAOYSA-N 3-bromocyclohexene Chemical compound BrC1CCCC=C1 AJKDUJRRWLQXHM-UHFFFAOYSA-N 0.000 description 1
- NMWSKOLWZZWHPL-UHFFFAOYSA-N 3-chlorobiphenyl Chemical group ClC1=CC=CC(C=2C=CC=CC=2)=C1 NMWSKOLWZZWHPL-UHFFFAOYSA-N 0.000 description 1
- LNGQLHZIYFQUIR-UHFFFAOYSA-N 3-chlorocyclohexene Chemical compound ClC1CCCC=C1 LNGQLHZIYFQUIR-UHFFFAOYSA-N 0.000 description 1
- BXSMMAVTEURRGG-UHFFFAOYSA-N 3-chlorohexane Chemical compound CCCC(Cl)CC BXSMMAVTEURRGG-UHFFFAOYSA-N 0.000 description 1
- PWRBCZZQRRPXAB-UHFFFAOYSA-N 3-chloropyridine Chemical compound ClC1=CC=CN=C1 PWRBCZZQRRPXAB-UHFFFAOYSA-N 0.000 description 1
- JFBMFWHEXBLFCR-UHFFFAOYSA-N 4-bromo-2-methylpyridine Chemical compound CC1=CC(Br)=CC=N1 JFBMFWHEXBLFCR-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- SVLZRCRXNHITBY-UHFFFAOYSA-N 4-chloro-1h-indole Chemical compound ClC1=CC=CC2=C1C=CN2 SVLZRCRXNHITBY-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- PVMNPAUTCMBOMO-UHFFFAOYSA-N 4-chloropyridine Chemical compound ClC1=CC=NC=C1 PVMNPAUTCMBOMO-UHFFFAOYSA-N 0.000 description 1
- BJUZAZKEDCDGRW-UHFFFAOYSA-N 5-bromo-2-methyl-1h-indole Chemical compound BrC1=CC=C2NC(C)=CC2=C1 BJUZAZKEDCDGRW-UHFFFAOYSA-N 0.000 description 1
- WZNRPMSUPREZGX-UHFFFAOYSA-N 7-chloro-2,3-dimethyl-1h-indole Chemical compound C1=CC=C2C(C)=C(C)NC2=C1Cl WZNRPMSUPREZGX-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VERCCDBWPZFKFE-UHFFFAOYSA-N C1C=CC=C1.Br.Br Chemical compound C1C=CC=C1.Br.Br VERCCDBWPZFKFE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910003514 Sr(OH) Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- HSDAJNMJOMSNEV-UHFFFAOYSA-N benzyl chloroformate Chemical compound ClC(=O)OCC1=CC=CC=C1 HSDAJNMJOMSNEV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XAVFZUKFLWOSOS-UHFFFAOYSA-N bis(dimethoxyphosphoryl)methane Chemical compound COP(=O)(OC)CP(=O)(OC)OC XAVFZUKFLWOSOS-UHFFFAOYSA-N 0.000 description 1
- LOXORFRCPXUORP-UHFFFAOYSA-N bromo-Cycloheptane Chemical compound BrC1CCCCCC1 LOXORFRCPXUORP-UHFFFAOYSA-N 0.000 description 1
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- KMJSGLZXFNSANB-UHFFFAOYSA-N chlorocycloheptane Chemical compound ClC1CCCCCC1 KMJSGLZXFNSANB-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RVOJTCZRIKWHDX-UHFFFAOYSA-N cyclohexanecarbonyl chloride Chemical compound ClC(=O)C1CCCCC1 RVOJTCZRIKWHDX-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- MSLICLMCQYQNPK-UHFFFAOYSA-N n-(4-bromophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Br)C=C1 MSLICLMCQYQNPK-UHFFFAOYSA-N 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010591 solubility diagram Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 239000004753 textile Substances 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)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3839—Polyphosphonic acids
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/342—Phosphonates; Phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
- D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
Definitions
- An object of this invention is to provide new and useful organic compounds of phosphorus containing a PC-P group in their molecules.
- a further object of this invention is to provide new and useful organic compounds of phosphorus containing a I335 PCP group in their molecules with the C group being a hydrophobic and/ or lipophilic groups.
- a further object of this invention is to provide new and useful organophosphonic acids, as well as their salts and esters.
- a more specific object of this invention is to provide new and useful organo-methylene diphosphonic acids or the salts thereof which exhibit, among other things, combined surfactancy, sequestering and deflocculating properties.
- a more specific object of this invention is to provide new and useful organo-met-hylene diphosphonate esters which exhibit, among other things, the unique ability of solubilizing water in water immiscible solvents.
- Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonic acids or the salts thereof.
- Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonic acids or the salts thereof which are suitable for use in aqueous systems.
- Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonate esters.
- a still further object of this invention is to provide detergent compositions containing organo-methylene diphosphonate esters which are suitable for use as dry-cleaning detergents in organic solvents.
- a still further object of this invention is to provide gasoline additive compositions containing organo-methylene diphosphonate esters.
- This invention is directed to new and useful organomethylene diphosphonic acid compounds, as well as the salts and esters thereof, said compounds having the gen eral formula.
- R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and carbon containing heterocyclic groups and X is selected fro-m the class con sisting of cations selected from the group consisting of hydrogen ions, alkali metal cations, alkaline earth metal cations, aluminum cations, ammonium ions and amine ions, and aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms.
- R and X represent groups containing carbon chains, such as aliphatic hydrocarbyl groups, or groups containing alkyl moieties, i.e., aralkyl groups
- carbon chains may be of a straight chain structure or branch chain structure.
- R and X when the represent aliphatic hydrocarbyl groups, such groups may be saturated or unsaturated.
- the compound of the instant invention should preferably contain not more than 25 carbon atoms associated with R and X (when X represents ester groups, and there are few, if any, end uses, in which'the foregoing groups contain more than a total of 50 carbon atoms.
- organo-methylene diphosphonic acids the salts of organo-rnethylene diphosphonic acids, and the esters of organo-methylene diphosphonic acids.
- the compounds of the invention can be prepared by various methods with the following methods presented as being representative of their preparation.
- the ester of the organo-methylene diphosphonic acids can be prepared by first forming a mctallo-derivative of a methylene diphosphonate ester and reacting this metallO ester derivative with an organo-halide to produce the desired organo-methylene diphosphonate ester.
- the reaction of the metallo-ester derivative with the organohalide is believed represented by the following equation:
- R represents the same groups as in the foregoing general Formula 1.
- metallo-derivatives of the tetraester methylene diphosphonate can be prepared in several ways.
- Group IA (alkali metals) ester derivatives and particularly the sodioand potassioester derivatives it is usually only necessary to react the alkali metal directly with the ester. The reaction is often exothermic so that, in most cases, it maybe necessary to bring the reactants together while cooling, to dilute the mixture with an inert solvent such as xylene, benzene, toluene, ether, dioxane, hexane and the like, or to add the sodium or potassium slowly to the esters in the inert solvent.
- an inert solvent such as xylene, benzene, toluene, ether, dioxane, hexane and the like, or to add the sodium or potassium slowly to the esters in the inert solvent.
- Group l-B metal derivatives and in particular the silver-ester derivative and cuprous-ester derivative; the Group II-B metal derivatives, and in particular the zinc-ester derivatives; and Group IV-A metal derivatives, and in particular the leadand tin-ester derivatives by methods which are similar to the foregoing methods. Because of the relative inexpensiveness and the ready availability of sodium and potassium and because of their rather straight forward reaction with the ester it is gen erally advantageous to form the sodioand po-tassio-ester derivatives and, therefore, sodium and potassium are the preferred metals for use in forming these ester derivatives.
- reaction of the metallo-ester derivatives with an organo halide is relatively straight forward. Oftentimes, however, it may be necessary to use temperatures above room temperature, i.e., about 25 C., in order to facilitate the reaction with temperatures of between about 70 C. to about 180 C. usually being sufficient. In most cases, depending on the temperature used, a definite precipitate forms, i.e., metal-halide, after a period of time of between about 10 minutes and about 4 hours.
- the precipitate may be removed by several well known methods, such as, filtration, centrifugation and decantation, or by dissolution with water and phase separation, and, if desired, the filtrate can thereafter be distilled to improve the purity of the organo-methylene diphosphonate ester.
- organo halides containing substituent groups such as, hydroxyl, carboxylic acid, and halides
- substituent groups such as, hydroxyl, carboxylic acid, and halides
- carboxylic acid groups can be protected by the well known method of esterification prior to the reaction and hydrolysis of the ester subsequent to the reaction.
- hydroxyl group can usually be protected by the well known method of ether formation using such materials as dihydropyrane, benzyl chloride, tritychloride and the like to form the ethers followed by removal of the protective groups by such methods as hydrolysis with dilute mineral acids, catalytic hydrogenation, or chemical reduction.
- the halide group of polyhalide compounds can usually be protected by conversion into an ether group, a common reactant being sodium alkoxide, and the ether group subsequently cleaved with a hydrogen halide to remove the protective ether groups.
- the organo-methylene diphosphonic acid can be prepared by the hydrolysis of the corresponding esters with a concentrated mineral acid. Generally, by refluxing the ester and a concentrated mineral acid, such as HCl or HBr, at reflux temperatures for a period of usually about five hours is all that is necessary for the hydrolysis.
- a concentrated mineral acid such as HCl or HBr
- the salts of the organo-methylene diphosphonic acids can be prepared by neutralization of the acids with a stoichiometric amount of a base or a salt of a volatile acid that contains essentially the desired cation.
- Bases or salts of volatile acids such as those containing an alkali metal, alkaline earth metal, aluminum, ammonia and amines are especially suited.
- one of organo-methylene diphosphonic acids can he neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like.
- organo-methylene diphosphonic acid titrates using a pH meter as a tribasic acid can be prepared by neutralization of the acids with a stoichiometric amount of a base and evaporating to dryness.
- the acids are titrated using a pH meter in the presence of a 10% NaCl solution they will titrate as tetra-basic acids.
- Example 1 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 65 C. After all of the potassium is used up about 179 grams of n-heptyl bromide is added dropwise to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated between about 100 C. and 140 C. for about 10 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester as a colorless liquid.
- Example 2 The ester prepared according to Example 1 is hydrolyzed to the acid by refluxing about 386 grams with about 600 ml. concentrated HCl for about 5 hours. Evaporation to dryness yields the acid, octylidene diphosphonic acid, C H CH[PO(OH) The equivalent weight of this product, by tritration, is found to be about 98.0 which compares favorably with the calculated value of about 91.3. Elemental analysis yields the following results:
- Trisodium octylidene diphosphonate C H CH[PO(ONa [PO(ONa) (OH)] is prepared by dissolving about 274 grams of free acid obtained as in Example 2 in about 1.2 liters of 10% NaOH solution and evaporating the aqueous solution to dryness at about 140 C. with the anhydrous form of the salt being formed.
- Example 4 Into a suitable reaction vessel about 39.1 grams potassium metal is added slowly to about 288 grams tetraethyl methylene diphosphonate in about 2.5 liters of Xylene. The temperature of the reaction vessel is maintained at about C. After all of the potassium is used up about 247 grams of n-dodecylbromide is added dropwise to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated at about C. for about 4 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester as a colorless liquid. Analysis of the P NMR spectra of the ester indicated tetraethyl tridecylidene diphosphonate,
- Example 5 Tetraethyl tridecylidene diphosphonate is hydrolyzed to the acid refluxing about 454 grams with about 600 ml. of concentrated HCl for about 2 to 3 hours. Evaporation to dryness yields the acid, tridecylidene diphosphonic acid, C H CH[PO(OH) which is analyzed with the following results:
- Example 5 is prepared by dissolving about 334 grams of the free acid obtained as in Example 5 in about 1 /2 liters of 10% NH OH solution and evaporating the aqueous solution to dryness at about 120 C. with the anhydrous form of the salt being formed.
- Example 7 2 5)2( 3) 4 9)2]2
- Example 8 Dicalcium cyclohexyl methylene diphosphonate
- C H CH[PO(OCaO)] J is prepared by dissolving about 322 grams of the free acid (cyclohexyl methylene diphosphonic acid), prepared generally by procedures used in Example 2, in about 1 liter of 20% Ca(OH) solution and evaporating the aqueous solu tion to dryness at about 120 C. with the anhydrous form of the salt being formed.
- the free acid cyclohexyl methylene diphosphonic acid
- Example 9 Tetraethyl benzyl methylene diphosphonate prepared generally by the procedures used in Example 1, is hydrolyzed to the acid by refluxing about 347 grams of the ester with about 800 ml. of concentrated HCl for about 4 hours. Evaporation to dryness yields the acid, benzyl methylene diphosphonic acid,
- Example 12 Tetraethyl acetophenone methylene diphosphonate CH C(O)C H -CH[PO(OC H prepare-d generally by procedures used in Example 1, is hydrolyzed to the acid by refluxing about 405 grams of the ester with about 800 ml. of concentrated MCl for about 3 hours. *Evaporation to dryness yields the acid, acetophenone methylene diphosphonic acid, CH C(O)C H -CH[PO(OH)
- Example 13 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 28 8 grams of tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C.
- Example 14 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams of tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C. After all of the potassium is used up about grams of (x-ClllOlOPYlIOl is added slowly to the reaction mixture. To ensure a satisfactory degree reaction the mixture is heated at about C. to about C. for about 6 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester, tetraethyl pyrryl-l-methylene diphosphonate,
- esters which can be reacted with metallic sources to form the metallo-ester derivatives, such as the potassio-ester derivatives, according to the procedures as illustrated by the foregoing examples include the following esters: tetramethyl methyl ene diphosphonate, tetra-n-hexyl methylene diphosphonate, tetra-isopropyl methylene diphosphonate, tetradodecyl methylene diphosphonate, tetra-hexadecyl methylene diphosphonate, tetra-toluyl methylene diphosphonate, tetra-xylyl methylene diphosphonate, and the like, as well as mixed esters, such as, diethyl-dibutyl methylene diphosphonate, diethyl-di-n-hexyl methylene diphosphonate, dimethyl-diethyl methylene diphosphonate and the following esters: te
- Alicyclic halide compounds include cyclopentyl bromide, cyclohexyl chloride, cycloheptanyl chloride, cycloheptanyl bromide, cyclopentadiene dibromide, cyclohexane carboxylic acid chloride, 1-chloro-1-methyl cyclohexane, 3-bromo-cyclohexene, 3-chloro-cyclohexene, 2- chloro-cyclopentadiene, 2-bromo-cycloheptanone, 1-2-dibromo cycloheptane, 1bromo-4tert-butyl-cyclohexane, 1- chloro-l-met-hyl cyclohexane, 1-2-dibromo cycloheptane, 1-chloro-3 methyl cyclohexane, and the like.
- Aryl halide compounds include the mono-cyclic arylhalide compounds, such as ch lorobenzene, 2-chloroaniline, 2-amino-4, 6-dichloro phenyl br-omobenzene, 4-bromo aniline and the like, as well as the polycyclic aryl halide compounds, such as, 3-chlo-robiphenyl, 4-amino-4-chloro biphenyl, 2-chloro-1-naphthal, 2-chloro-anthraquinone, 1- chl oro-naphthalene, l-bromo-naphthalene, 2 bromo biphenyl, and the like.
- Alkaryl halide compounds include benzyl chloride, ⁇ 3- phenyl ethyl chloride, 4-methyl benzyl chloride, 3-rnethyl benzyl chloride, Z-methyl benzyl chloride, 2-chlorobenzyl chloride, 4-chlorobenzyl chloride, 3-chlorobenzyl chloride, 4-isopropy1 benzyl chloride, m-xylene dichloride, a-chl-oro acetophenone, benzyl chloroformate, benzyl bromide, B-phenyl ethyl bromide, Z-bromo benzyl bromide, 3-nitro benzyl bromide and the like.
- Aralkyl halide compounds include 2-chlorotoluene, 3- chlorotoluene, 4-chlorotoluene, l-chloro-Z-ethyl benzene, 2-ch loro-2-vinyl benzene, 1-chloro-2-isopropyl benzene, 2-chloro-4-isop1'opyl-l-methyl benzene, p-chloro benzoic acid, 2-chloro-4-octyl phenol, 2-chloro-4-nonyl phenol, 2-chloro-4-dodecy1 phenol, 2-benzyl-4-chlorophenol, 2- bromotoluene, 1-bromo-4-ethyl benzene, 4-bromoacetanilide, 4-bromoacetophenone, phenaryl bromide, 4- bromobenzoic acid and the like.
- Heterocyclic halide compounds include N-chlorosuccinimide, N-bromo succinimide, 2-chloropyridine, 2- chloroquinaline, 2bromo-5- nitro furan, 2-bromo-5-methyl furan, S-bromo indole, 5-bromo-2-methyl indole, 4-bromo-2-picoline, 3-chloropyridine, 4-chloropyridine, 3-bro- D mo-thiophene, 2-bromo-3,4-dinitro thiophene, 2-chloro thiophene, 2-bromofuran, 3,4-dichloro-tetrahydrofuran, 3,4-dichloro-2,S-diphenyl furan, S-bromoindole, 4chloroindole, 7-chloro-2,3-dimethyl indole, 2-chloro-1,4,6-trimethyl indole and the like.
- bases or salts of volatile acids which can be reacted with the free acids to produce salt compounds of the instant invention according to the procedures as illustrated by the foregoing examples include the inorganic alkali metal, alkaline earth metal and aluminum salts, oxides and hydroxides, such as, NaCl, NaNO Na O, Na CO KOH, K 0, KCl, K CO KNO LiOH, LiCl, LlNO3, Ll2CO CSOH, CsCl, CSNO3, CS2CO3, CaCl CaO, CaCO MgCl MgO, MgCO BaCO BaCl Ba(OH) Ba(NO SrCA SrCl Sr(OH) Al(OH A1 Al(NO and amines, such as, ethyl amine, diethylamine, propyl amine, propylene diamine, diethylene triamine, hexyl amine, 2-ethylhexyl amine and the like.
- oxides and hydroxides such as, NaCl, NaNO
- organo-methylene diphosphonic acids or the salts thereof were found to exhibit not only good deflocculating or dispersing properties and sequestration properties but also good surfactancy properties. It is highly unusual for all of these properties to be effectively exhibited by the same compound. As can be appreciated, such compounds can advantageously be utilized in applications which can use the foregoing properties, such as, detergent compositions.
- R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from 5 to 20 carbon atoms and Z is a cation selected from the group consisting of hydrogen in conventional amounts such as is normally used with detergent compositions and which is generally about 5% concentration or below.
- esters of organo-methylene diphosphonic acids were found not only to be substantially miscible with water but also highly soluble in organic solvents, such as hydrocarbon solvent, i.e. hexane and pentane, carbon tetra chloride, haloethylene solvents (perchloroethylene), ethers, alcohols, and the like.
- organic solvents such as hydrocarbon solvent, i.e. hexane and pentane, carbon tetra chloride, haloethylene solvents (perchloroethylene), ethers, alcohols, and the like.
- the esters were found to impart a solubilizing. action to water in water-immiscible solvents, such as many of the previously mentioned solvents. This totally unexpected property renders them highly useful as gasoline de-icer additives and along with their surfactancy properties renders them useful as dry cleaning detergents.
- the unique ability to impart a solubilizing action to water in water-immiscible solvents can be utilized in many and
- esters of higher alkylidene diphosphonic acids are preferred in applications which use the combined surfactancy and/or water solubilizing properties. These compounds are of the following formula:
- R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from to carbon atoms and R R R and R are selected from the class consisting of alkyl groups of from 1 to 20 carbon atoms, aryl hydrocarbyl groups and alkaryl groups with the lower alkyl groups being especially preferred.
- ester compounds of the instant invention are useful in gasoline as de-icer additives and are preferably used in amounts of from .005 to 5% by weight.
- An advantageous feature of these deicer additives is their ability to function either wholly as the primary additive for surface ignition control or in conjunction with other known phosphorus additives for surface ignition control.
- ester compounds of the instant invention can be used as either the primary surfactant or in conjunction with other surfactants.
- the primary surfactant When used as substantially the primary surfactant with many of the common organic solvents, such as, Stoddards solvent and perchloroethylene, amounts within the range of .05% to 10% by weight are usually sufficient with amounts about 2% by weight being preferred.
- ester compounds of the instant invention may also be used as extractants for metals in an aqueous-organic solvent system.
- R is selected from the class consisting of aliphatic hydrocarbyl groups of from 7 to 30 carbon atoms and alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and
- X is selected from the class consisting of cations selected from the group consisting of hydrogen ions, alkali metal cations, alkaline earth metal cations, aluminum cations, ammonium ions and amine ions, and aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms.
- a diphosphonic acid having the formula wherein R is selected from the class consisting of aliphatic hydrocarbyl groups of from 7 to 30 carbon atoms and alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is hydrogen.
- a salt of a diphosphonic acid said salt having the formula wherein R is selected from the class consisting of aliphatic hydrocarbyl groups of from 7 to 30 carbon atoms and alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is selected from the class consisting of alkali metal cations, alkaline earth metal cations, aluminum cations, ammonium ions, and amine ions. 4.
- An ester of a diphosphonic acid said ester having the formula X0 0 R 0 0X ⁇ ll 1 ll/ PC-P XO/ r I oX wherein R is selected from the class consisting of aliphatic hydrocarbyl groups of from 7 to 30 carbon atoms and alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is selected from the class consisting of aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms.
- a diphosphonic compound having the formula ZO H OZ wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl groups containing from 7 to 20 carbon atoms and Z is a cation selected from the group consisting of hydrogen ion, alkali metal cations, alkaline earth metal cations, aluminum cations, ammonium ions and amine ions.
- a salt of a diphosphonic acid said salt having the formula ZO ⁇ O R 1+1 ZO Z wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl groups containing from 7 to 20 carbon atoms and Z is a cation selected from the class consisting of alkali metal cations, alkaline earth metal cations, aluminum cations, ammonium ions, and amine ions.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DENDAT1302557D DE1302557B (zh) | 1963-04-09 | ||
US271607A US3299123A (en) | 1963-04-09 | 1963-04-09 | Substituted methylene diphosphonic acids and salts and esters thereof |
DE19641302929D DE1302929B (zh) | 1963-04-09 | 1964-04-08 | |
FR970088A FR1394386A (fr) | 1963-04-09 | 1964-04-08 | Nouveaux acides organo-méthylène diphosphoniques, leurs sels et esters |
US590449A US3414393A (en) | 1963-04-09 | 1966-08-29 | Gasoline compositions containing diphosphonates |
US578500A US3518200A (en) | 1963-04-09 | 1966-09-12 | Organic phosphorus compounds,compositions containing same,and uses thereof |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US271607A US3299123A (en) | 1963-04-09 | 1963-04-09 | Substituted methylene diphosphonic acids and salts and esters thereof |
US590449A US3414393A (en) | 1963-04-09 | 1966-08-29 | Gasoline compositions containing diphosphonates |
US57850066A | 1966-09-12 | 1966-09-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3299123A true US3299123A (en) | 1967-01-17 |
Family
ID=27402394
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US271607A Expired - Lifetime US3299123A (en) | 1963-04-09 | 1963-04-09 | Substituted methylene diphosphonic acids and salts and esters thereof |
US590449A Expired - Lifetime US3414393A (en) | 1963-04-09 | 1966-08-29 | Gasoline compositions containing diphosphonates |
US578500A Expired - Lifetime US3518200A (en) | 1963-04-09 | 1966-09-12 | Organic phosphorus compounds,compositions containing same,and uses thereof |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US590449A Expired - Lifetime US3414393A (en) | 1963-04-09 | 1966-08-29 | Gasoline compositions containing diphosphonates |
US578500A Expired - Lifetime US3518200A (en) | 1963-04-09 | 1966-09-12 | Organic phosphorus compounds,compositions containing same,and uses thereof |
Country Status (2)
Country | Link |
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US (3) | US3299123A (zh) |
DE (2) | DE1302929B (zh) |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3400176A (en) * | 1965-11-15 | 1968-09-03 | Procter & Gamble | Propanepolyphosphonate compounds |
US3463835A (en) * | 1965-10-05 | 1969-08-26 | Plains Chem Dev Co | Aromatic polyphosphonic acids,salts and esters |
US3475486A (en) * | 1966-09-12 | 1969-10-28 | Monsanto Co | Process for preparing phosphonic acids |
US3475293A (en) * | 1964-09-22 | 1969-10-28 | Monsanto Co | Electrodeposition of metals |
US3488419A (en) * | 1965-12-08 | 1970-01-06 | Procter & Gamble | Oral compositions for calculus retardation |
US3518200A (en) * | 1963-04-09 | 1970-06-30 | Monsanto Co | Organic phosphorus compounds,compositions containing same,and uses thereof |
US3609075A (en) * | 1968-06-25 | 1971-09-28 | Procter & Gamble | Cleaning and softening detergent compositions |
US3617576A (en) * | 1970-04-13 | 1971-11-02 | Monsanto Co | Methods of scale inhibition |
US3624188A (en) * | 1968-10-25 | 1971-11-30 | Procter & Gamble | Hypohalogenation of tetramethyl and tetraethyl methylenediphosphonates and trihydrocarbyl phosphonoacetates |
US3678154A (en) * | 1968-07-01 | 1972-07-18 | Procter & Gamble | Oral compositions for calculus retardation |
US3683080A (en) * | 1970-08-28 | 1972-08-08 | Procter & Gamble | Compositions for inhibiting anomalous deposition and mobilization of calcium phosphate in animal tissue |
US3846420A (en) * | 1969-11-19 | 1974-11-05 | Henkel & Cie Gmbh | Process for the preparation of 1-aminoalkane-1,-diphosphonic acids and their salts |
US3846483A (en) * | 1970-04-13 | 1974-11-05 | Monsanto Co | Substituted ethane diphosphonic acids and salts and esters thereof |
US3925456A (en) * | 1973-08-27 | 1975-12-09 | Henkel & Cie Gmbh | Cyclic aminophosphonic acids |
US3940436A (en) * | 1970-04-13 | 1976-02-24 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
US3992332A (en) * | 1974-08-22 | 1976-11-16 | Hemson Joseph Zenon | Liquid composition for fabric treatment |
USRE29182E (en) * | 1965-12-08 | 1977-04-12 | The Procter & Gamble Company | Oral composition for calculus retardation |
US4020091A (en) * | 1965-10-28 | 1977-04-26 | Plains Chemical Development Co. | Chelation |
US4116990A (en) * | 1970-04-30 | 1978-09-26 | Plains Chemical Development Co. | Chelation |
US4138431A (en) * | 1978-06-29 | 1979-02-06 | Nalco Chemical Company | Reaction of α-phosphorus containing carboxylic acids with phosphorous acid to prepare scale and corrosion inhibitors |
US4157364A (en) * | 1977-10-25 | 1979-06-05 | Buckman Laboratories, Inc. | Process for preparing dimethylaminomethylenebis(phosphonic acid) |
US4309364A (en) * | 1979-02-13 | 1982-01-05 | Symphar S.A. | Diphosphonates |
US4416877A (en) * | 1979-02-13 | 1983-11-22 | Symphar S.A. | Anti-atherosclerotic pharmaceutical compositions containing diphosphonate compounds |
US4719203A (en) * | 1985-11-13 | 1988-01-12 | Boehringer Mannheim Gmbh | Diphosphonic acid derivatives, processes for the preparation thereof and pharmaceutical compositions containing them |
US4746654A (en) * | 1982-07-29 | 1988-05-24 | Sanofi | Anti-inflammatory products derived from methylene-diphosphonic acid, and process for their preparation |
US4818774A (en) * | 1986-03-10 | 1989-04-04 | Occidental Chemical Corporation | Organophosphorus compounds |
US5043330A (en) * | 1988-03-31 | 1991-08-27 | Symphar S.A. | Phenol substituted gem-diphosphonate derivatives, process for their preparation and pharmaceutical compositions containing them |
US5157027A (en) * | 1991-05-13 | 1992-10-20 | E. R. Squibb & Sons, Inc. | Bisphosphonate squalene synthetase inhibitors and method |
US5449804A (en) * | 1989-11-06 | 1995-09-12 | Zaosheng; Xiao | Diphosphonate compounds, their preparation and application |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4148603A (en) * | 1974-10-04 | 1979-04-10 | Henkel Kommanditgesellschaft Auf Aktien | Method of washing textiles and composition containing inorganic silicates and polycarboxylates and/or polyphosphonates |
US5332728A (en) * | 1992-11-23 | 1994-07-26 | Bristol-Myers Squibb Company | Method for treating a fungal infection |
US20060191851A1 (en) * | 2005-02-25 | 2006-08-31 | Mizuno William G | Method for treating feedwater, feedwater treatment composition, and apparatus for treating feedwater |
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US2339096A (en) * | 1941-05-22 | 1944-01-11 | Cities Service Oil Co | Solvent composition and method of cleaning lubricated apparatus |
US2634288A (en) * | 1951-01-10 | 1953-04-07 | Virginia Carolina Chem Corp | Tetraalkyl esters of alkane diphosphonic acids |
US2651656A (en) * | 1950-04-17 | 1953-09-08 | Us Rubber Co | Process of preparing tetraalkyl esters of 1, 2-ethanediphosphonic acid |
US2793945A (en) * | 1954-01-11 | 1957-05-28 | Exxon Research Engineering Co | Residual fuels |
US2889213A (en) * | 1954-01-06 | 1959-06-02 | Phillips Petroleum Co | Engine fuel containing anti-icing additives |
US2904514A (en) * | 1951-07-06 | 1959-09-15 | Metallgesellschaft Ag | Textile cleaning solution |
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US2897071A (en) * | 1953-06-30 | 1959-07-28 | Ethyl Corp | Gasoline fuels |
US2999739A (en) * | 1956-03-28 | 1961-09-12 | Ethyl Corp | Antiknock fluids |
US3093672A (en) * | 1960-10-03 | 1963-06-11 | Monsanto Chemicals | Diphosphonate alkyl esters |
NL290315A (zh) * | 1962-03-20 | |||
DE1302557B (zh) * | 1963-04-09 | 1971-08-26 |
-
0
- DE DENDAT1302557D patent/DE1302557B/de active Pending
-
1963
- 1963-04-09 US US271607A patent/US3299123A/en not_active Expired - Lifetime
-
1964
- 1964-04-08 DE DE19641302929D patent/DE1302929B/de active Pending
-
1966
- 1966-08-29 US US590449A patent/US3414393A/en not_active Expired - Lifetime
- 1966-09-12 US US578500A patent/US3518200A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US2339096A (en) * | 1941-05-22 | 1944-01-11 | Cities Service Oil Co | Solvent composition and method of cleaning lubricated apparatus |
US2651656A (en) * | 1950-04-17 | 1953-09-08 | Us Rubber Co | Process of preparing tetraalkyl esters of 1, 2-ethanediphosphonic acid |
US2634288A (en) * | 1951-01-10 | 1953-04-07 | Virginia Carolina Chem Corp | Tetraalkyl esters of alkane diphosphonic acids |
US2904514A (en) * | 1951-07-06 | 1959-09-15 | Metallgesellschaft Ag | Textile cleaning solution |
US2889213A (en) * | 1954-01-06 | 1959-06-02 | Phillips Petroleum Co | Engine fuel containing anti-icing additives |
US2793945A (en) * | 1954-01-11 | 1957-05-28 | Exxon Research Engineering Co | Residual fuels |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3518200A (en) * | 1963-04-09 | 1970-06-30 | Monsanto Co | Organic phosphorus compounds,compositions containing same,and uses thereof |
US3475293A (en) * | 1964-09-22 | 1969-10-28 | Monsanto Co | Electrodeposition of metals |
US3463835A (en) * | 1965-10-05 | 1969-08-26 | Plains Chem Dev Co | Aromatic polyphosphonic acids,salts and esters |
US4020091A (en) * | 1965-10-28 | 1977-04-26 | Plains Chemical Development Co. | Chelation |
US3400176A (en) * | 1965-11-15 | 1968-09-03 | Procter & Gamble | Propanepolyphosphonate compounds |
US3502585A (en) * | 1965-11-15 | 1970-03-24 | Procter & Gamble | Detergent compositions containing propanepolyphosphonate compounds |
US3488419A (en) * | 1965-12-08 | 1970-01-06 | Procter & Gamble | Oral compositions for calculus retardation |
USRE29182E (en) * | 1965-12-08 | 1977-04-12 | The Procter & Gamble Company | Oral composition for calculus retardation |
US3475486A (en) * | 1966-09-12 | 1969-10-28 | Monsanto Co | Process for preparing phosphonic acids |
US3609075A (en) * | 1968-06-25 | 1971-09-28 | Procter & Gamble | Cleaning and softening detergent compositions |
US3678154A (en) * | 1968-07-01 | 1972-07-18 | Procter & Gamble | Oral compositions for calculus retardation |
US3624188A (en) * | 1968-10-25 | 1971-11-30 | Procter & Gamble | Hypohalogenation of tetramethyl and tetraethyl methylenediphosphonates and trihydrocarbyl phosphonoacetates |
US3846420A (en) * | 1969-11-19 | 1974-11-05 | Henkel & Cie Gmbh | Process for the preparation of 1-aminoalkane-1,-diphosphonic acids and their salts |
US3846483A (en) * | 1970-04-13 | 1974-11-05 | Monsanto Co | Substituted ethane diphosphonic acids and salts and esters thereof |
US3940436A (en) * | 1970-04-13 | 1976-02-24 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
US3617576A (en) * | 1970-04-13 | 1971-11-02 | Monsanto Co | Methods of scale inhibition |
US4116990A (en) * | 1970-04-30 | 1978-09-26 | Plains Chemical Development Co. | Chelation |
US3683080A (en) * | 1970-08-28 | 1972-08-08 | Procter & Gamble | Compositions for inhibiting anomalous deposition and mobilization of calcium phosphate in animal tissue |
US3925456A (en) * | 1973-08-27 | 1975-12-09 | Henkel & Cie Gmbh | Cyclic aminophosphonic acids |
US3992332A (en) * | 1974-08-22 | 1976-11-16 | Hemson Joseph Zenon | Liquid composition for fabric treatment |
US4157364A (en) * | 1977-10-25 | 1979-06-05 | Buckman Laboratories, Inc. | Process for preparing dimethylaminomethylenebis(phosphonic acid) |
US4138431A (en) * | 1978-06-29 | 1979-02-06 | Nalco Chemical Company | Reaction of α-phosphorus containing carboxylic acids with phosphorous acid to prepare scale and corrosion inhibitors |
US4309364A (en) * | 1979-02-13 | 1982-01-05 | Symphar S.A. | Diphosphonates |
US4371527A (en) * | 1979-02-13 | 1983-02-01 | Symphar S.A. | Therapeutic process with diphosphonate compounds |
US4416877A (en) * | 1979-02-13 | 1983-11-22 | Symphar S.A. | Anti-atherosclerotic pharmaceutical compositions containing diphosphonate compounds |
US4746654A (en) * | 1982-07-29 | 1988-05-24 | Sanofi | Anti-inflammatory products derived from methylene-diphosphonic acid, and process for their preparation |
US4876248A (en) * | 1982-07-29 | 1989-10-24 | Sanofi | Anti-inflammatory products derived from methylene-diphosphonic acid, and process for their preparation |
US4719203A (en) * | 1985-11-13 | 1988-01-12 | Boehringer Mannheim Gmbh | Diphosphonic acid derivatives, processes for the preparation thereof and pharmaceutical compositions containing them |
AU584759B2 (en) * | 1985-11-13 | 1989-06-01 | Boehringer Mannheim Gmbh | New diphosphonic acid derivatives, processes for the preparation thereof and pharmaceutical compositions containing them |
US4818774A (en) * | 1986-03-10 | 1989-04-04 | Occidental Chemical Corporation | Organophosphorus compounds |
US5043330A (en) * | 1988-03-31 | 1991-08-27 | Symphar S.A. | Phenol substituted gem-diphosphonate derivatives, process for their preparation and pharmaceutical compositions containing them |
US5128331A (en) * | 1988-03-31 | 1992-07-07 | Symphar S.A. | Method for lowering plasma lipid levels or blood pressure |
US5449804A (en) * | 1989-11-06 | 1995-09-12 | Zaosheng; Xiao | Diphosphonate compounds, their preparation and application |
US5157027A (en) * | 1991-05-13 | 1992-10-20 | E. R. Squibb & Sons, Inc. | Bisphosphonate squalene synthetase inhibitors and method |
Also Published As
Publication number | Publication date |
---|---|
US3414393A (en) | 1968-12-03 |
DE1302557B (zh) | 1971-08-26 |
DE1302929B (zh) | 1971-12-30 |
US3518200A (en) | 1970-06-30 |
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