US3414393A - Gasoline compositions containing diphosphonates - Google Patents
Gasoline compositions containing diphosphonates Download PDFInfo
- Publication number
- US3414393A US3414393A US590449A US59044966A US3414393A US 3414393 A US3414393 A US 3414393A US 590449 A US590449 A US 590449A US 59044966 A US59044966 A US 59044966A US 3414393 A US3414393 A US 3414393A
- Authority
- US
- United States
- Prior art keywords
- ester
- groups
- methylene
- diphosphonate
- compounds
- 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
- 239000000203 mixture Substances 0.000 title description 26
- -1 hydrogen ions Chemical class 0.000 description 53
- 239000002253 acid Substances 0.000 description 40
- 150000002148 esters Chemical class 0.000 description 37
- 150000001875 compounds Chemical class 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 27
- 150000007513 acids Chemical class 0.000 description 23
- 229940102859 methylene diphosphonate Drugs 0.000 description 22
- 238000000034 method Methods 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 239000003599 detergent Substances 0.000 description 15
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000011591 potassium Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 238000001914 filtration Methods 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
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 125000002877 alkyl aryl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 239000002585 base 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
- 230000008020 evaporation Effects 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- HWZUDASOMGNLSM-UHFFFAOYSA-N O=P1OCOP(=O)O1 Chemical compound O=P1OCOP(=O)O1 HWZUDASOMGNLSM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 230000009919 sequestration Effects 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000005108 dry cleaning Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PQKOJNVKGNOTKZ-UHFFFAOYSA-N 1,2-dibromocycloheptane Chemical compound BrC1CCCCCC1Br PQKOJNVKGNOTKZ-UHFFFAOYSA-N 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 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
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011156 evaluation Methods 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
- 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
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 125000001424 substituent group Chemical group 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
- 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 1
- 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
- VQRBXYBBGHOGFT-UHFFFAOYSA-N 1-(chloromethyl)-2-methylbenzene Chemical compound CC1=CC=CC=C1CCl VQRBXYBBGHOGFT-UHFFFAOYSA-N 0.000 description 1
- LZBOHNCMCCSTJX-UHFFFAOYSA-N 1-(chloromethyl)-3-methylbenzene Chemical compound CC1=CC=CC(CCl)=C1 LZBOHNCMCCSTJX-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
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-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
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-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
- XGCKOSFYXBAPQM-UHFFFAOYSA-N 1-chloro-3,3-dimethylbutane Chemical compound CC(C)(C)CCCl XGCKOSFYXBAPQM-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
- 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
- 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
- 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
- JFNPFFAEYZRVJS-UHFFFAOYSA-N 2-bromocycloheptan-1-one Chemical compound BrC1CCCCCC1=O JFNPFFAEYZRVJS-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
- NXXHAWKBICGUCK-UHFFFAOYSA-N 2-chloro-2-methylpentane Chemical compound CCCC(C)(C)Cl NXXHAWKBICGUCK-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-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
- WMPPDTMATNBGJN-UHFFFAOYSA-N 2-phenylethylbromide Chemical compound BrCCC1=CC=CC=C1 WMPPDTMATNBGJN-UHFFFAOYSA-N 0.000 description 1
- AJKDUJRRWLQXHM-UHFFFAOYSA-N 3-bromocyclohexene Chemical compound BrC1CCCC=C1 AJKDUJRRWLQXHM-UHFFFAOYSA-N 0.000 description 1
- COVFMDKBWYLRSV-UHFFFAOYSA-N 3-chloro-2,2-dimethylbutane Chemical compound CC(Cl)C(C)(C)C COVFMDKBWYLRSV-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
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004135 Bone phosphate Substances 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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 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
- 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
- 125000003545 alkoxy group Chemical group 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
- KVLCHQHEQROXGN-UHFFFAOYSA-N aluminium(1+) Chemical compound [Al+] KVLCHQHEQROXGN-UHFFFAOYSA-N 0.000 description 1
- 229940007076 aluminum cation Drugs 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 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
- 238000005282 brightening Methods 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
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 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
- 239000013256 coordination polymer Substances 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
- 238000004821 distillation 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
- 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
- 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 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
- 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
- 239000007787 solid Substances 0.000 description 1
- 238000010591 solubility diagram Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004448 titration 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)]
- C07F9/3804—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
- the present invention relates to and covers gasoline compositions which contain organo-methylene diphosphonic esters such as for example tetramethyl methylene diphosphonate.
- a further object of this invention is to provide new and useful organic compounds of phosphorus containing a group in their molecules with the C35 group being a hydrophobic and/ or lipophilic group.
- 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 defiocculating properties.
- a more specific object of this invention is to provide new and useful organo-methylene 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 inveniton 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.
- 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 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.
- R and X represent groups containing carbon chains, such as aliphatic hydrocarbyl groups, or groups containing alkyl moieties, i.e., aralkyl groups, such carbon chains may be of a straight chain structure or branched chain structure.
- R and X when they represent aliphatic hydrocarbyl groups, such groups may be saturated or unsaturated.
- R can also contain substituents, such as, hydroxyl, halides, i.e., fluoride, chloride, bromide and iodide, alkoxy groups, ester groups, ether groups, nitro groups, sulfonyl groups, amide groups, amino groups, carboxyl groups, nitroso groups and the like as long as they do not materially interfere with the hydrophilic and/or lipophilic nature of groups.
- substituents such as, hydroxyl, halides, i.e., fluoride, chloride, bromide and iodide, alkoxy groups, ester groups, ether groups, nitro groups, sulfonyl groups, amide groups, amino groups, carboxyl groups, nitroso groups and the like as long as they do not materially interfere with the hydrophilic and/or lipophilic nature of groups.
- the compounds of the instant invention should preferably contain not more than 25 carbon atoms associated with R and X (when X represents ester
- organo-methylene diphosphonic acids the salts of organo-methylene 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 metallo-derivative of a methylene diphosphonate ester and reacting this metalloester derivative with an organo-halide to produce the desired organo-methylene diphosphonate ester.
- the reaction of the metallo-ester derivative with the organo-halide is believed represented by the following equation:
- R represents the same groups as in the foregoing general Formula 1.
- metallo-derivatives of the tetra-ester methylene diphosphonate can be prepared in several ways.
- Group IA (alkali metals) ester derivatives and particularly the sodioand potassio-ester 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 may be 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.
- an inert solvent such as xylene, benz
- Group II-B metal derivatives and in particular the zincester derivative; 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 generally advantageous to form the sodioand potassio-ester derivatives and, therefore, sodium and potassium are the preferred metals for use in forming these ester derivatives.
- reaction (2) the reaction of the metallo-ester derivatives with an organo halide, i.e., reaction (2), is relatively straight forward. Often times, however, it may be necessary to use temperatures above room temperature, i.e., about 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., metalhalide, 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 to protect these groups during the reaction.
- 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 hydroylsis 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 action.
- 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 be 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 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 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. Analysis of the P n.m.r.
- 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 titration, 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 tetra-ethyl 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 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,
- Tetraethyl tridecylidene diphosphonate is hydrolyzed to the acid by 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.
- C12H25CH[PO(ONH4)2] 4) 1' is prepared by dissolving about 334 grams of the free acid obtained as in Example in about 1 /2 liters of 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 Into a suitable reaction vessel about 102 grams of 3- chloro-3-rnethyl pentane is added slowly to a potassiobutyl ester derivative reaction mixture prepared as in Example 1. To ensure a satisfactory degree reaction the mixture is heated at about 120 C. for about 6 hours. After filtering the potassium chloride, the reaction product is purified by distillation yielding tetrabutyl fl-diethylfl-methylethylidene diphosphonate,
- C H CH[ PO(OCaO) 1 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 Ca(OH) solution and evaporating the aqueous solution to dryness at about 120 C. with the anhydrous form of the salt being formed.
- EXAMPLE 12 Tetraethyl acetophenone methylene diphosphonate CH C( O)C H CH [PO( OC I-I prepared generally by procedures use-d in Example 1, is hydrolyzed to the acid by refluxing aout 405 grams of the ester with about 800 ml. of concentrated HCl for about 3 hours. Evaporation to dryness yields the acid, acetophenone methylene diphosphonic acid, CH C(O)C H -CH[PO(OH) l 6 EXAMPLE 13 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 333 grams of octadecylbromide is added slowly to the reaction mixture. To ensure a satisfactory degree reaction the mixture is heated at about 120 C. to 140 C. for about 10 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester, tetraethyl nonadecylidene diphosphonate, C H CH[PO(OC H Elemental analysis of the product gives the following result.
- 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 u-chloropyrrole 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-1-methylene diphosphonate, C H N -CH [P(O)(OC H5)2].
- esters which can be reacted with metallic sources to form the metallo-cster derivatives, such as the potassio-ester derivatives, according to the procedures as illustrated by the foregoing examples include the following esters: tetramethyl methyl methylene diphosphonate, tetra-n-hexyl methylene diphosphonate, tetra-isopropyl methylene diphosphonate, tetra-dodeoyl methylene diphosphonate, tetrahexadecyl methylene diphosphonate, tetra-toluyl methylene diphosphonate, tetra-xylyl methylene diphosphonate, and the like, as well as mixed esters, such as, diethyldibutyl methylene diphosphonate, diethyl-di-n-hexyl methylene diphosphonate, dimethyl-diethyl methylene diphosphonate and the following esters: te
- Alicyclic halide oompounds include cyclopentyl bromide, cyclohexyl chloride, cycloheptanyl chloride, cycloheptanyl bromide, cyclopentadiene dibromide, cyclohexane carboxylic acid chloride, l-chloro-l-methyl cyclohexane, 3-bromo-cyclohexene, 3-chloro-cyclohexene, 2- chloro-cyclopentadiene, 2-bromo-cycloheptanone, 1,2-dibromo cycloheptane, 1-b-romo-4-tertbutyl-cyclohexane, l-chloro-l-methyl cyclohexane, 1,2-dibromo cycloheptane, 1-chloro-3-methyl cyclohexane, and the like.
- Aryl halide compounds include the mono-cyclic arylhalide compounds, such as, chlorobenzene, 2-chloroaniline, 2-amino-4, 6-dichloro phenol bromobenzene, 4-bromo aniline and the like, as well as the polycyclic aryl halide compounds, such as, 3-chloro bip-henyl, 4- amino-4-chloro biphenyl, 2-chloro-1-napthal, 2-ch1oroanthraquinone, l-chloro-napthalene, l-bromo-napthalene, 2-bromo biphenol, and the like.
- Alkaryl halide compounds include benzyl chloride, fl-phenyl ethyl chloride, 4-methyl benzyl chloride, 3- methyl benzyl chloride, 2-methyl benzyl chloride, 2-chlorobenzyl chloride, 4-chlorobenzyl chloride, 3-chlorobenzyl chloride, 4-isopropyl 'benzyl chloride, m-xylene dichloride, a-chloro acetophenone, benzyl chloroformate, benzyl bromide, ,B-phenyl ethyl bromide, 2-bromo 'benzyl 2-bromo biphenyl, and the like.
- Aralkyl halide compounds include 2-chlorotoluene, 3- chlorotoluene, 4-chlorotoluene, 1-chloro-2-ethyl benzene, 2-chloro-2-vinyl benzene, l-chloro-Z-isopropyl benzene, 2-chloro-4-isopropyl-l-methyl benzene, p-chloro benzoic acid, 2-chloro-4-octyl phenol, 2-chloro-4-nonyl phenol, 2-chloro-4-dodecyl phenol, 2-benzyl-4-chlorophenol, 2- bromotoluene, 1-bron1o-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, 2-bromo-5-nitro furan, 2-bromo-5- methyl furan, S-bromo indole, S-bromo-Z-methyl indole, 4-bromo-2-picoline, 3-chloropyridine, 4-chloropyridine, 3-bromothiophene, 2-bromo-3, 4-dinitro thiophene, 2- chloro thiophene, 2-bromofuran, 3,4dichloro-tetrahydrofuran, 3,4-dichloro-2, S-diphenyl furan, S-bromo-indole, 4-chloro indole, 7-chloro-2, 3-dimethyl indole, 2-chloro-l, 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 C KOH, K 0, KC], K CO KNO LiOH, LiCl, LiNO Li CO CsOH, CsCl, CsNO CsCO CaCl CaO, CaCO Mgcl MgO, MgCO BaCO BaCl Ba(OH) Ba(NO CrCo SrCl Sr(OH) A1(0H A1 0 Al(NO and amines, such as, ethyl amine, diethylamine, propyl amine, propylene diamine, diethylene triamine, hexyl amine, Z-ethylhexyl amine and the like.
- oxides and hydroxides such as, NaCl, NaNO Na O, Na
- 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, a
- detergent compositions such as, detergent compositions.
- detergent applications such as textile cleaning including synthetic textiles and hard surface cleaning
- the higher alkalidene diphosphonic acids or the salts thereof are preferred in applications which use the combined surfactancy, sequestration and defiocculating 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 20 carbon atoms and Z is a cation selected from the group consisting of hydrogen ion, alkali metal cation, alkaline earth metal cation, aluminum cation, ammonium ion, and amine ion.
- the compounds of the instant invention are preferably formulated with other components which may include other surface active compounds (actives) as Well as builders such as sodium tripolyphosphate and tetrapotassium pyrophosphate, antiredeposition agents such as carboxymethyl cellulose and the like, brightening agents, perfumes and the like, in amounts between about 5% to 50% by weight of the detergent composition.
- actives surface active compounds
- builders such as sodium tripolyphosphate and tetrapotassium pyrophosphate
- antiredeposition agents such as carboxymethyl cellulose and the like
- brightening agents perfumes and the like
- compounds illustrative of the invention exhibit the ability to lower the surface tension of water (4).
- Compounds (2) and (3) compared very favorably with sodium dodecylbenzene sulfonate (5), a widely used surfactant, when used in molar concentrations of 5X10- and 10-
- compound (1) exhibited no appreciable surfactancy ability since a compound exhibiting a surface tension above about at molar concentrations of 5 10- and 10- is not usually, regarded as a surfactant.
- compounds of this invention are particularly well suited for use in detergent compositions.
- 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 varied
- esters of higher alkylidene diphosphonic acids are preferred in applications which use the combined surfactany 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 20 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 de-icer additives, by reason of their phosphorus content, 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 sutficient with amounts about 2% by weight being preferred.
- ester compounds of the instant invention may also be as extractants for metals in an aqueousorganic solvent system.
- a gasoline composition consisting essentially of (a) gasoline and (b) from about 0.005% to about 5.0% by weight, based on the total weight of said composition of an ester of an organo-methylene diphosphonic acid, said ester 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 aliphatic hydrocarbyl, aryl, alkaryl, and aralkyl groups having up to 30 carbon atoms.
- a gasoline composition consisting essentially of (a) gasoline and (b) from about 0.005% to about 5.0% by weight, based on the total weight of said composition of an ester of a higher alkylidene diphosphonic acid, said ester having the formula wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl groups containing from 5 to 20 carbon atoms and R R R and R are selected from the class consisting of alkyl groupsof from 1 to 20 carbon atoms, and aryl hydrocarbyl groups and alkaryl groups having up to 30 carbon atoms.
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Description
United States Patent 3,414,393 GASOLINE COMPOSITIONS CONTAINING DIPHOSPHONATES Steven J. Fitch, Creve Coeur, and Riyad R. Irani, Florissant, Mo., assignors to Monsanto Company, a corporation of Delaware No Drawing. Original application Feb. 9, 1963, Ser. No. 271,607, now Patent No. 3,299,123. Divided and this application Aug. 29, 1966, Ser. No. 590,449
2 Claims. ('CI. 44-76) ABSTRACT OF THE DISCLOSURE The present invention relates to and covers gasoline compositions which contain organo-methylene diphosphonic esters such as for example tetramethyl methylene diphosphonate.
PCP
group in their molecules.
A further object of this invention is to provide new and useful organic compounds of phosphorus containing a group in their molecules with the C35 group being a hydrophobic and/ or lipophilic group.
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 defiocculating properties.
A more specific object of this invention is to provide new and useful organo-methylene 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 inveniton 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.
3,414,393 Patented Dec. 3, 1968 XOOROOX wherein: 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 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. When the symbols R and X represent groups containing carbon chains, such as aliphatic hydrocarbyl groups, or groups containing alkyl moieties, i.e., aralkyl groups, such carbon chains may be of a straight chain structure or branched chain structure. For the symbols R and X when they represent aliphatic hydrocarbyl groups, such groups may be saturated or unsaturated. The above mentioned groups which are represented by R can also contain substituents, such as, hydroxyl, halides, i.e., fluoride, chloride, bromide and iodide, alkoxy groups, ester groups, ether groups, nitro groups, sulfonyl groups, amide groups, amino groups, carboxyl groups, nitroso groups and the like as long as they do not materially interfere with the hydrophilic and/or lipophilic nature of groups. For most end use applications the compounds 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.
These compounds can be characterized quite generally has having a P-CP linkage in their molecules and are generically described in this specification by the general terms organo-methylene diphosphonic acids, the salts of organo-methylene 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 metallo-derivative of a methylene diphosphonate ester and reacting this metalloester derivative with an organo-halide to produce the desired organo-methylene diphosphonate ester. The reaction of the metallo-ester derivative with the organo-halide is believed represented by the following equation:
wherein R represents the same groups as in the foregoing general Formula 1.
In general, metallo-derivatives of the tetra-ester methylene diphosphonate can be prepared in several ways. When preparing the Group IA (alkali metals) ester derivatives and particularly the sodioand potassio-ester 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 may be 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. In some cases'it may be necessary to employ all of the immediately -silver-ester derivative and cuprousester derivative; the
Group II-B metal derivatives, and in particular the zincester derivative; 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 generally advantageous to form the sodioand potassio-ester derivatives and, therefore, sodium and potassium are the preferred metals for use in forming these ester derivatives.
In general, the reaction of the metallo-ester derivatives with an organo halide, i.e., reaction (2), is relatively straight forward. Often times, however, it may be necessary to use temperatures above room temperature, i.e., about 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., metalhalide, 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.
It may be necessary, however, when using organo halides containing substituent groups, such as, hydroxyl, carboxylic acid, and halides to protect these groups during the reaction. Usually the 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. Also the 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 hydroylsis with dilute mineral acids, catalytic hydrogenation, or chemical reduction. In addition, by using well known methods 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.
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 action. Bases or salts of volatile acids such as those containing an alkali metal, alkaline earth metal, aluminum, ammonia and amines are especially suited. For example, to make a sodium salt, one of organo-methylene diphosphonic acids can be neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like. It should be noted that organo-methylene diphosphonic acid titrates using a pH meter as a tribasic acid, however, the tetra salts can be prepared by neutralization of the acids with a stoichiometric amount of a base and evaporating to dryness. In addition, it has been found if the acids are titrated using a pH meter in the presence of a 10% NaCl solution they will titrate as tetra-basic acids.
The following examples are presented to illustrate the invention, with parts by weight being used in the examples unless otherwise indicated.
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 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 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. Analysis of the P n.m.r. spectra of the ester indicates tetraethyl octylidene diphosphonate, C H CH[PO(OC H with a small amount of impurity 5 of tetraethyl methylene diphosphonate. Elemental analysis yields the following results.
Calculated: C, 49.80%; H, 9.39%. Found: C, 46.82%; H, 9.51%.
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 titration, is found to be about 98.0 which compares favorably with the calculated value of about 91.3. Elemental analysis yields the following results.
Calculated: C, 35.00%; H, 7.29%. Found: C, 33.17%; H, 6.89%.
EXAMPLE 3 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 tetra-ethyl 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 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,
Elemental analysis of this product yields the following results.
Calculated: C, 55.3%; H, 10.2%; P, 13.6%. Found: C, 54.28%; H, 10.58%; P, 12.97%.
EXAMPLE 5 Tetraethyl tridecylidene diphosphonate is hydrolyzed to the acid by 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.
Calculated: C, 45.34%; H, 8.78%; P, 17.99%. Found: C, 44.86%; H, 8.71%; P, 17.90%.
5 EXAMPLE 6 Tri-ammonium tridecylidene diphosphonate,
C12H25CH[PO(ONH4)2] 4) 1' is prepared by dissolving about 334 grams of the free acid obtained as in Example in about 1 /2 liters of 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 Into a suitable reaction vessel about 102 grams of 3- chloro-3-rnethyl pentane is added slowly to a potassiobutyl ester derivative reaction mixture prepared as in Example 1. To ensure a satisfactory degree reaction the mixture is heated at about 120 C. for about 6 hours. After filtering the potassium chloride, the reaction product is purified by distillation yielding tetrabutyl fl-diethylfl-methylethylidene diphosphonate,
EXAMPLE 8 Dicalcium cyclohexyl methylene diphosphonate,
C H CH[ PO(OCaO) 1 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 Ca(OH) solution and evaporating the aqueous solution to dryness at about 120 C. with the anhydrous form of the salt being formed.
EXAMPLE 9 Tetraethyl benzyl methylene diphosphonate CSH4CH[P(O) 2' 5)2]2 prepared generally by the procedures used in Example 1, is hydrolyzed to the acid by refluxing about 347 grams of the ester with about 80-0 ml. of concentrated HCl for about 4 hours. Evaporation to dryness yields the acid, benzyl methylene diphosphonic acid,
C5H4CH 2] 2 EXAMPLE l0 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 479 grams tetraphenyl 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 233 grams of 2-bromobiphenyl is added slowly to the reaction mixture. T 0 ensure a satisfactory degree of reaction the mixture is heat-ed at about 100 C. for about 8' hours. After filtering the potassium bromide, the reaction product is distilled yielding the ester, tetraphenyl biphenyl methylene diphosphonate,
s s s 4 lI s s) 2l2 EXAMPLE l1 Tetraethyl dodecylbenzyl methylene diphosphonate, (C H )C H CH[PO-(OC H prepared generally by procedure used in Example 1, is hydrolyzed to the acid by refluxing about 425 grams of the ester with about 800 m1. of concentrated HCl for about 4 hours. Evaporation to dryness yields the acid, dodecylbenzyl methylene diphosphonic acid,
EXAMPLE 12 Tetraethyl acetophenone methylene diphosphonate CH C( O)C H CH [PO( OC I-I prepared generally by procedures use-d in Example 1, is hydrolyzed to the acid by refluxing aout 405 grams of the ester with about 800 ml. of concentrated HCl for about 3 hours. Evaporation to dryness yields the acid, acetophenone methylene diphosphonic acid, CH C(O)C H -CH[PO(OH) l 6 EXAMPLE 13 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 333 grams of octadecylbromide is added slowly to the reaction mixture. To ensure a satisfactory degree reaction the mixture is heated at about 120 C. to 140 C. for about 10 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester, tetraethyl nonadecylidene diphosphonate, C H CH[PO(OC H Elemental analysis of the product gives the following result.
Calculated: C, 60.5%; H, 11.73%. Found: C, 63.07%; H, 11.49%.
Nuclear magnetic resonance analysis gives a P shift in p.p.m. of 23.9.
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 u-chloropyrrole 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-1-methylene diphosphonate, C H N -CH [P(O)(OC H5)2].
Other methylene diphosphonate esters which can be reacted with metallic sources to form the metallo-cster derivatives, such as the potassio-ester derivatives, according to the procedures as illustrated by the foregoing examples include the following esters: tetramethyl methyl methylene diphosphonate, tetra-n-hexyl methylene diphosphonate, tetra-isopropyl methylene diphosphonate, tetra-dodeoyl methylene diphosphonate, tetrahexadecyl methylene diphosphonate, tetra-toluyl methylene diphosphonate, tetra-xylyl methylene diphosphonate, and the like, as well as mixed esters, such as, diethyldibutyl methylene diphosphonate, diethyl-di-n-hexyl methylene diphosphonate, dimethyl-diethyl methylene diphosphonate and the like.
Other halide compounds which can be reacted with the metallo-ester derivatives, such as the potassio-ester derivatives, according to procedures as illustrated by the foregoing example to form compounds of the instant invention include aliphatic hydrocarbyl halide compounds, such as, 3-chloro-2-rnethyl butene-l; 3-chloro-2-methyl butene-2; 2-chloro-2-methyl pentane; 3-chloro-2,2-dimethyl butane; 4-chloro-2,2-dimethyl butane; 3-chloro- 2,2,3-trimethyl butane; 3-chlorohexane; n-hexyl chloride; n-undecyl chloride; n-hexadecyl chloride; n-hexyl bromide; n-octy1 bromide; n-dodecyl bromide; n-tetradecyl bromide; l-bromo-n-caproic acid; 2-bromo hexanoic acid and the like.
Alicyclic halide oompounds include cyclopentyl bromide, cyclohexyl chloride, cycloheptanyl chloride, cycloheptanyl bromide, cyclopentadiene dibromide, cyclohexane carboxylic acid chloride, l-chloro-l-methyl cyclohexane, 3-bromo-cyclohexene, 3-chloro-cyclohexene, 2- chloro-cyclopentadiene, 2-bromo-cycloheptanone, 1,2-dibromo cycloheptane, 1-b-romo-4-tertbutyl-cyclohexane, l-chloro-l-methyl cyclohexane, 1,2-dibromo cycloheptane, 1-chloro-3-methyl cyclohexane, and the like.
Aryl halide compounds include the mono-cyclic arylhalide compounds, such as, chlorobenzene, 2-chloroaniline, 2-amino-4, 6-dichloro phenol bromobenzene, 4-bromo aniline and the like, as well as the polycyclic aryl halide compounds, such as, 3-chloro bip-henyl, 4- amino-4-chloro biphenyl, 2-chloro-1-napthal, 2-ch1oroanthraquinone, l-chloro-napthalene, l-bromo-napthalene, 2-bromo biphenol, and the like.
Alkaryl halide compounds include benzyl chloride, fl-phenyl ethyl chloride, 4-methyl benzyl chloride, 3- methyl benzyl chloride, 2-methyl benzyl chloride, 2-chlorobenzyl chloride, 4-chlorobenzyl chloride, 3-chlorobenzyl chloride, 4-isopropyl 'benzyl chloride, m-xylene dichloride, a-chloro acetophenone, benzyl chloroformate, benzyl bromide, ,B-phenyl ethyl bromide, 2-bromo 'benzyl 2-bromo biphenyl, and the like.
Aralkyl halide compounds include 2-chlorotoluene, 3- chlorotoluene, 4-chlorotoluene, 1-chloro-2-ethyl benzene, 2-chloro-2-vinyl benzene, l-chloro-Z-isopropyl benzene, 2-chloro-4-isopropyl-l-methyl benzene, p-chloro benzoic acid, 2-chloro-4-octyl phenol, 2-chloro-4-nonyl phenol, 2-chloro-4-dodecyl phenol, 2-benzyl-4-chlorophenol, 2- bromotoluene, 1-bron1o-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, 2-bromo-5-nitro furan, 2-bromo-5- methyl furan, S-bromo indole, S-bromo-Z-methyl indole, 4-bromo-2-picoline, 3-chloropyridine, 4-chloropyridine, 3-bromothiophene, 2-bromo-3, 4-dinitro thiophene, 2- chloro thiophene, 2-bromofuran, 3,4dichloro-tetrahydrofuran, 3,4-dichloro-2, S-diphenyl furan, S-bromo-indole, 4-chloro indole, 7-chloro-2, 3-dimethyl indole, 2-chloro-l, 4,6-trimethyl indole and the like.
Other 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 C KOH, K 0, KC], K CO KNO LiOH, LiCl, LiNO Li CO CsOH, CsCl, CsNO CsCO CaCl CaO, CaCO Mgcl MgO, MgCO BaCO BaCl Ba(OH) Ba(NO CrCo SrCl Sr(OH) A1(0H A1 0 Al(NO and amines, such as, ethyl amine, diethylamine, propyl amine, propylene diamine, diethylene triamine, hexyl amine, Z-ethylhexyl amine and the like.
Quite unexpectedly 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, a
such as, detergent compositions. In many detergent applications such as textile cleaning including synthetic textiles and hard surface cleaning, the ability of the detergent composition to remove the soil, keep the soil suspended in the washing medium, as well as, exerting a water softening effect in the washing medium by sequestration of calcium and magnesium ions, is of paramount importance.
The higher alkalidene diphosphonic acids or the salts thereof are preferred in applications which use the combined surfactancy, sequestration and defiocculating properties. These compounds are of the following formula:
ROOZ
Z 0 o 2 wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from to 20 carbon atoms and Z is a cation selected from the group consisting of hydrogen ion, alkali metal cation, alkaline earth metal cation, aluminum cation, ammonium ion, and amine ion.
As used in detergent compositions, the compounds of the instant invention are preferably formulated with other components which may include other surface active compounds (actives) as Well as builders such as sodium tripolyphosphate and tetrapotassium pyrophosphate, antiredeposition agents such as carboxymethyl cellulose and the like, brightening agents, perfumes and the like, in amounts between about 5% to 50% by weight of the detergent composition. The resulting detergent composi tion is generally effective when used in aqueous systems in conventional amounts such as is normally used with detergent compositions and which is generally about 5% concentration or below.
Compounds illustrative of the invention were tested for surfactancy properties by determining surface tension measurements with a du Nuoy Tensiometer in dis tilled water at room temperature. The compounds tested were at concentrations believed representative of detergent concentrations used in actual applications. The results of the test are tabulated below.
TAB LE I Surface Tension (dyne/cn.) at
As can be observed from the above table, compounds illustrative of the invention, i.e., (2) and (3), exhibit the ability to lower the surface tension of water (4). Compounds (2) and (3) compared very favorably with sodium dodecylbenzene sulfonate (5), a widely used surfactant, when used in molar concentrations of 5X10- and 10- It should be noted that compound (1) exhibited no appreciable surfactancy ability since a compound exhibiting a surface tension above about at molar concentrations of 5 10- and 10- is not usually, regarded as a surfactant. As can be appreciated, therefore, by reason of their surfactancy, compounds of this invention are particularly well suited for use in detergent compositions.
Compounds illustrative of the invention were tested for deflocculating properties in a carefully controlled kaolin slurry. The kaolin used in the evaluation was essentially free of impurities and was placed in an aqueous slurry with a solids contents about 68%. The slurry throughout the evaluation was maintained at a pH of about 7 with NaOH or HCl. The apparent viscosity was determined with a Stormer Viscometer at 300 rpm. The results of the tests are tabulated below.
TABLE 2 Apparent viscosity in centipoises at 300 r.p.m. Stonner at indicated As can be observed from the above table, minor amounts of the compounds illustrative of the invention, i.e., (2) and (3) deflocculated a plastic slurry into a flowable slurry. In addition, compounds (2) and (3) compared very favorably with sodium tripolyphosphate (4), a widely used deflocculant, and compound (1) when 9 used in amounts of about .1 and .15 weight based on a dry clay basis.
Compounds illustrative of the invention were tested for sequestration properties. The conditions of the test were to dissolve .25 gms., of the tetrasodium salt of the compound of the instant invention and .25 gms. of
in 250 ml. of Water and adjust the pH to 12 with NaOH. To the solution is added 0.1 M Ca(NO until a cloudy endpoint, i.e., the precipitation of CaC O is achieved. In order to calculate the pounds of calcium sequestered by 100 pounds of material tested, the volume of 0.1M Ca(NO used, in cc. units, is multiplied by 1.6. The results of the test are tabulated below.
TABLE 3 Lbs. calcium/100 lbs. of compound (1) Tetrasodium octylidene diphosphonate Compound:
C H CH[PO(ONa) (2) Tetrasodium tridecylidene diphosphonate C12H25CH[PO(ON3.)2]2
As can be observed from the above table, compounds illustrative of the instant invention, i.e., (1) and (2) exhibited the ability to sequester calcium, thus indicating their beneficial use in aqueous systems containing such IOIIS.
The 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. Also, 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. As can be appreciated, however, the unique ability to impart a solubilizing action to water in water-immiscible solvents can be utilized in many and varied applications and, therefore, the foregoing mentioned applications are merely indicative of their use.
The esters of higher alkylidene diphosphonic acids are preferred in applications which use the combined surfactany and/or water solubilizing properties. These compounds are of the following formula:
wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from to 20 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.
Because of the complexity of the ternary solubility diagram of the esters of the instant inventionwaterwaterimmiscible solvents the following is set-forth for example purposes only.
A solution of cc. of hexane and 5 cc. of the following esters of the higher alkylidene diphosphonic acids dissolves the amounts of water at room temperature indicated in Table 4. The water was added dropwise until permanent cloudiness or phase separation was observed. The tabulated results are presented in the following table.
Table 4 Compound: H O added (cc.)
(1) Tetra ethyl octylidene diphosphonate C H CH [PO(OC H .5 (2) Tetra ethyl tridecylidene diphosphonate C H CH [PO(OC H 2.5
It should be noted that the foregoing example solutions exhibited no phase separation at the end of a one week period of standing nor was there a phase separation after the solutions had been centrifuged at 5,000 r.p.m. for one hour indicating that the water Was completely dissolved in the water-immiscible solvent. It should further be noted that tetraethyl methylene diphosphonate, CH [PO(OC H did not impart a solubilizing action to water in a water-immiscible solvent.
As previously mentioned the 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 de-icer additives, by reason of their phosphorus content, 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.
As dry cleaning additives the ester compounds of the instant invention can be used as either the primary surfactant or in conjunction with other surfactants. 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 sutficient with amounts about 2% by weight being preferred.
In addition, the ester compounds of the instant invention may also be as extractants for metals in an aqueousorganic solvent system.
Although the compounds of the instant invention as well as their uses have been described with a degree of particularity, the invention herein is intended to be limited only by the claims set forth hereinafter.
What is claimed is:
1. A gasoline composition consisting essentially of (a) gasoline and (b) from about 0.005% to about 5.0% by weight, based on the total weight of said composition of an ester of an organo-methylene diphosphonic acid, said ester 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 aliphatic hydrocarbyl, aryl, alkaryl, and aralkyl groups having up to 30 carbon atoms.
2. A gasoline composition consisting essentially of (a) gasoline and (b) from about 0.005% to about 5.0% by weight, based on the total weight of said composition of an ester of a higher alkylidene diphosphonic acid, said ester having the formula wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl groups containing from 5 to 20 carbon atoms and R R R and R are selected from the class consisting of alkyl groupsof from 1 to 20 carbon atoms, and aryl hydrocarbyl groups and alkaryl groups having up to 30 carbon atoms.
References Cited UNITED STATES PATENTS 2,897,071 7/1959 Gilbert 4469 2,999,739 9/1961 Heron 4469 3,093,672 6/1963 Miller 4469 DANIEL E. WYMAN, Primary Examiner.
W. I. SHINE, Assistant Examiner.
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FR970088A FR1394386A (en) | 1963-04-09 | 1964-04-08 | New organomethylene diphosphonic acids, their salts and esters |
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US590449A US3414393A (en) | 1963-04-09 | 1966-08-29 | Gasoline compositions containing diphosphonates |
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DE (2) | DE1302929B (en) |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1302557B (en) * | 1963-04-09 | 1971-08-26 | ||
DE1496916B1 (en) * | 1964-09-22 | 1969-10-23 | Monsanto Co | Cyanide-free, galvanic bath and process for the deposition of galvanic coatings |
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 |
USRE29182E (en) * | 1965-12-08 | 1977-04-12 | The Procter & Gamble Company | Oral composition for calculus retardation |
NL149701C (en) * | 1965-12-08 | 1981-05-15 | Procter & Gamble | METHOD FOR PREPARING AN AGENT TOOTHIC CARE, WHICH INCLUDES A PHOSPHONIC ACID DERIVATIVE AS AN ACTIVE INGREDIENT, AND FORMED TOOTHIC CARE. |
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 |
DE1958123C3 (en) * | 1969-11-19 | 1978-09-28 | Henkel Kgaa, 4000 Duesseldorf | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids or their salts |
US3617576A (en) * | 1970-04-13 | 1971-11-02 | Monsanto Co | Methods of scale inhibition |
US3705191A (en) * | 1970-04-13 | 1972-12-05 | 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 |
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 |
DE2343195C2 (en) * | 1973-08-27 | 1981-11-19 | Henkel KGaA, 4000 Düsseldorf | Cyclic aminophosphonic acids and processes for their preparation |
US3992332A (en) * | 1974-08-22 | 1976-11-16 | Hemson Joseph Zenon | Liquid composition for fabric treatment |
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 |
US4163733A (en) * | 1977-10-25 | 1979-08-07 | Buckman Laboratories, Inc. | Synergistic compositions for corrosion and scale control |
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 |
GB2043072B (en) * | 1979-02-13 | 1983-11-23 | Symphar Sa | Diphosphonate compounds |
US4416877A (en) * | 1979-02-13 | 1983-11-22 | Symphar S.A. | Anti-atherosclerotic pharmaceutical compositions containing diphosphonate compounds |
FR2531088B1 (en) * | 1982-07-29 | 1987-08-28 | Sanofi Sa | ANTI-INFLAMMATORY PRODUCTS DERIVED FROM METHYLENEDIPHOSPHONIC ACID AND THEIR PREPARATION METHOD |
DE3540150A1 (en) * | 1985-11-13 | 1987-05-14 | Boehringer Mannheim Gmbh | NEW DIPHOSPHONIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS |
US4818774A (en) * | 1986-03-10 | 1989-04-04 | Occidental Chemical Corporation | Organophosphorus compounds |
CH675422A5 (en) * | 1988-03-31 | 1990-09-28 | Symphar Sa | |
US5233092A (en) * | 1989-11-06 | 1993-08-03 | Xiao Zaosheng | 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 |
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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
NL77048C (en) * | 1951-07-06 | |||
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 |
CA729145A (en) * | 1962-03-20 | 1966-03-01 | The Procter & Gamble Company | Built liquid detergent |
DE1302557B (en) * | 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 (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Also Published As
Publication number | Publication date |
---|---|
US3518200A (en) | 1970-06-30 |
DE1302929B (en) | 1971-12-30 |
US3299123A (en) | 1967-01-17 |
DE1302557B (en) | 1971-08-26 |
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