US3363032A - Long chain aliphatic benzylphosphonic acids, esters and salts - Google Patents
Long chain aliphatic benzylphosphonic acids, esters and salts Download PDFInfo
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- US3363032A US3363032A US374255A US37425564A US3363032A US 3363032 A US3363032 A US 3363032A US 374255 A US374255 A US 374255A US 37425564 A US37425564 A US 37425564A US 3363032 A US3363032 A US 3363032A
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- -1 aliphatic benzylphosphonic acids Chemical class 0.000 title description 34
- 150000003839 salts Chemical class 0.000 title description 10
- 150000002148 esters Chemical class 0.000 title description 9
- 239000002253 acid Substances 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical group COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QNYTWBDDXXEESX-UHFFFAOYSA-N 1-phenylhexadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCC(P(O)(O)=O)C1=CC=CC=C1 QNYTWBDDXXEESX-UHFFFAOYSA-N 0.000 description 2
- SEDJFLCFMPQLJE-UHFFFAOYSA-N 1-phenyltridecylphosphonic acid Chemical compound CCCCCCCCCCCCC(P(O)(O)=O)C1=CC=CC=C1 SEDJFLCFMPQLJE-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005108 dry cleaning Methods 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- AQPLTFFFQYQGOT-UHFFFAOYSA-N 1-chlorohexadecylbenzene Chemical compound C(CCCCCCCCCCCCCC)C(C1=CC=CC=C1)Cl AQPLTFFFQYQGOT-UHFFFAOYSA-N 0.000 description 1
- ISXDOPCKEDRLAY-UHFFFAOYSA-N 1-chlorotridecylbenzene Chemical compound CCCCCCCCCCCCC(Cl)C1=CC=CC=C1 ISXDOPCKEDRLAY-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
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 229910013553 LiNO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon bond
-
- 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
- C07F9/3882—Arylalkanephosphonic acids
-
- 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
Definitions
- This invention relates to organic compounds of phosphorus and more particularly to long chain aliphatic benzylphosphonic acids as well as the esters and salts thereof.
- An object of this invention is to provide new and useful organic compounds of phosphorus.
- Another object of this invention is to provide long chain aliphatic benzylphosphonic acids as well as the erties and foam stability.
- This invention is directed to new and useful long chain aliphatic benzylphosphonic acids, as well as the esters and water-soluble salts thereof, said compounds having the general formula R OX wherein: R is an aliphati group containing from 6 to 20 carbon atoms and X is selected from the class consisting of hydrogen, lower alkyl radicals containing from '1 to 5 carbon atoms, and cations selected from the group consisting of alkali metal, ammonium, and amines.
- R representing aliphatic groups
- such groups may be straight chain or branch chain and may be saturated or unsaturated, and preferably are alkyl groups and ethylenically unsaturated (especially alkenyl groups) and 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, amine groups, carboxyl groups, nitroso groups and the like as long as they 3,363,032 Patented Jan. 9, 1968 "ice do not materially interfere with the hydrophobic nature of the aliphatic group.
- substituents such as, hydroxyl, halides, i.e., fluoride, chloride, bromide and iodide, alkoxy groups, ester groups, ether groups, nitro groups, sulfonyl groups, amide groups, amine groups, carb
- alkali metal such may include lithium, sodium, potassium and the like, as well as mixtures of these, although sodium and potassium are preferred.
- amines such are preferably low molecular weight amines, i.e., having a molecular weight below about 200, and more particularly the alkyl amines, alkylene amines and alkanol amines containing not more than 2 amine groups.
- alkylbenzylphosphonic acids and the water-soluble salts thereof having the general formula ll CHz-P wherein: R is an alkyl group containing from 8 to 18 carbon atoms and X is selected from the class consisting of hydrogen, and cations selected from the group consisting of alkali metal, ammonium, and amines.
- R is an alkyl group containing from 8 to 18 carbon atoms and X is selected from the class consisting of hydrogen, and cations selected from the group consisting of alkali metal, ammonium, and amines.
- the preferred alkali metal salts and amine salts are those described hereinbefore for Formula 1.
- the compounds of the invention can be prepared by various methods with the following method presented as being representative of their preparation.
- a long chain aliphatic benzyl halide preferably chloride
- a tri-alkyl phosphite preferably a tri-lower alkyl phosphite, such as methyl, ethyl, propyl, butyl or pentyl
- R represents the same groups as in the foregoing general Formula 1.
- temperatures in the range of from about C. to about 250 C. are preferred as well as an excess of phosphite of from about 20 to about 60 weight percent. Reaction times are usually several hours, i.e., from about 2 hours to about 15 hours.
- the long chain aliphatic benylphosphonic acids 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 5 hours is all that is necessary for the hydrolysis.
- a concentrated mineral acid such as HCl or HBr
- the salts of the long chain aliphatic benyl phosphonic 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.
- a stoichiometric amount of a base or a salt of a volatile acid that contains essentially the desired cation For example, to make a sodium salt, the long chain aliphatic benylphosphonic acid can be neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like.
- Example 1 Into a suitable reaction vessel are charged about 275 parts of pentadecylbenzylchloride and about 204 parts of triethyl phosphite. The temperature is raised to about C. for about 7 hours at which time the temperature is slowly raised to about C. When the evolution of ethyl chloride has essentially stopped (about 4 hours later), the reaction product is distilled in a molecular still at about 180-190 C. to yield di-ethyl pentadecylbenzylphosphonate.
- Example 2 The ester of Example 1 is hydrolyzed with excess concentrated HCl for about 34 hours on a steam bath.
- the product usually forms in a gelatinous layer which can be recovered by decanting the aqueous layer and dissolving the product (residue) in ethanol and evaporating the ethanol.
- Example 3 Disodium pentadecylbenzylphosphonate is prepared by dissolving the free acid obtained as in Example 2 in hot water (about 70 C.) maintained at a high pH (about 11 or 12) with NaOH and evaporating the aqueous solution to dryness at about 140 C.
- Example 4 Into a suitable reaction vessel are charged about 302 parts of dodecylbenzylchloride and about 165 parts of tri-ethyl phosphite. The temperature is raised to about 140 C. for about 10 hours at which time the temperature is slowly raised to about 160 C. When the evolution of ethyl chloride has essentially stopped (about 4 hours later) the reaction product is distilled in a molecular still at about 155-165 C. to yield diethyl dodecylbenzylphosphonate.
- Example 5 The ester of Example 4 is hydrolyzed with excess concentrated HCl for about 30 hours on a steam bath. The product layer is recovered in substantially the same manner as in Example 2 to yield dodecylbenzylphosphonic acid.
- Exampleo Dipotassium dodecylbenzylphosphonate is prepared by dissolving the free acid obtained as in Example 5 in hot water (about 70 C.) maintained at a high pH (about 11 or 12) with KOH and evaporating the aqueous solution to dryness at about 140 C.
- 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 such inorganic alkali metal salts, oxides and hydroxides as NaNO Na O, Na CO KOH, K 0, K C KNO LiOH, LiNO Li C0 and the like, ammonium compounds such as (NH CO NH OH, and the like, and amines such as ethyl amine, diethyl amine, propyl amine, ethanol amine, triethanol amine, propylene diamine, propanol amine, 2-ethylhexyl amine, and the like.
- ester compounds of the present invention are useful in minor amounts (usually from about 0.005% to 5% 4 by weight) in gasoline as gasoline de-icer additives and are useful with many organic solvents such as perchloroethylene in amounts from about 05% to 10% by Weight as dry-cleaning surfactants.
- R is selected from the class consisting of alkyl and alkenyl radicals containing from 6 to 20 carbon atoms.
- a salt compound of a long chain aliphatic benzylphosphonic acid said salt having the formula CHri wherein: R is selected from the class consisting of alkyl and alkenyl groups containing from 6 to 20 carbon atoms and X is a cation selected from the group consisting of alkali metal, ammonium and low molecular weight alkyl amines, alkylene amines and alkanol amines containing not more than 2 amine groups.
- R is an alkyl group containing from 8 to 18 carbon atoms and X is selected from the class consisting of hydrogen and cations selected from the group consistmg of alkali metal, ammonium, and low molecular weight alkyl amines, alkylene amines and alkanol amines-coutammg not more than 2 amine groups.
- Alkylbenzylphosphonic acid having the formula fi/OH CH2-P wherein: R is an alkyl group containing from 8 to 18 carbon atoms.
- a salt compound of alkylbenzylphosphonic acid said salt having the formula 8. Pentadecylbenzylphosphonic acid.
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- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
United States Patent 3 363,032 LONG CHAIN ALIPHZATIC BENZYLPHOSPHONIC ACIDS, ESTERS AND SALTS Steven J. Fitch, St. Louis, Mo., assignor to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed June 11, 1964, Ser. No. 374,255 13 Claims. (Cl. 260-961) ABSTRACT OF THE DISCLOSURE Organo-phosphorus compounds useful as surface active agents, dry cleaning detergents in organic solvents and gasoline deicer additives are described having the formula 0 0X II/ wherein: R is an alkyl or alkenyl group containing from 6 to 20 carbon atoms and X is selected from the class consisting of hydrogen, lower alkyl radicals containing from 1 to 5 carbon atoms, and cations selected from the group consisting of alkali metal, ammonium and low molecular weight alkyl amines, alkylene amines and alkanol amines containing not more than 2 amine groups.
This invention relates to organic compounds of phosphorus and more particularly to long chain aliphatic benzylphosphonic acids as well as the esters and salts thereof.
An object of this invention is to provide new and useful organic compounds of phosphorus.
Another object of this invention is to provide long chain aliphatic benzylphosphonic acids as well as the erties and foam stability.
Other objects will be apparent from the following description.
This invention is directed to new and useful long chain aliphatic benzylphosphonic acids, as well as the esters and water-soluble salts thereof, said compounds having the general formula R OX wherein: R is an aliphati group containing from 6 to 20 carbon atoms and X is selected from the class consisting of hydrogen, lower alkyl radicals containing from '1 to 5 carbon atoms, and cations selected from the group consisting of alkali metal, ammonium, and amines.
For the symbol R representing aliphatic groups, such groups may be straight chain or branch chain and may be saturated or unsaturated, and preferably are alkyl groups and ethylenically unsaturated (especially alkenyl groups) and 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, amine groups, carboxyl groups, nitroso groups and the like as long as they 3,363,032 Patented Jan. 9, 1968 "ice do not materially interfere with the hydrophobic nature of the aliphatic group. When the symbol X represents alkali metal, such may include lithium, sodium, potassium and the like, as well as mixtures of these, although sodium and potassium are preferred. When the symbol X represents amines, such are preferably low molecular weight amines, i.e., having a molecular weight below about 200, and more particularly the alkyl amines, alkylene amines and alkanol amines containing not more than 2 amine groups.
Especially preferred as surface active agents in aqueous systems are the alkylbenzylphosphonic acids and the water-soluble salts thereof having the general formula ll CHz-P wherein: R is an alkyl group containing from 8 to 18 carbon atoms and X is selected from the class consisting of hydrogen, and cations selected from the group consisting of alkali metal, ammonium, and amines. The preferred alkali metal salts and amine salts are those described hereinbefore for Formula 1.
The compounds of the invention can be prepared by various methods with the following method presented as being representative of their preparation.
In general, a long chain aliphatic benzyl halide (preferably chloride) and a tri-alkyl phosphite (preferably a tri-lower alkyl phosphite, such as methyl, ethyl, propyl, butyl or pentyl) can be reacted to form esters according to the reaction believed represented by the following equation:
OEt
+ EtCl OEt wherein: R represents the same groups as in the foregoing general Formula 1.
Usually temperatures in the range of from about C. to about 250 C. are preferred as well as an excess of phosphite of from about 20 to about 60 weight percent. Reaction times are usually several hours, i.e., from about 2 hours to about 15 hours.
The long chain aliphatic benylphosphonic acids 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 5 hours is all that is necessary for the hydrolysis.
The salts of the long chain aliphatic benyl phosphonic 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. For example, to make a sodium salt, the long chain aliphatic benylphosphonic acid can be neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like.
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 are charged about 275 parts of pentadecylbenzylchloride and about 204 parts of triethyl phosphite. The temperature is raised to about C. for about 7 hours at which time the temperature is slowly raised to about C. When the evolution of ethyl chloride has essentially stopped (about 4 hours later), the reaction product is distilled in a molecular still at about 180-190 C. to yield di-ethyl pentadecylbenzylphosphonate.
Example 2 The ester of Example 1 is hydrolyzed with excess concentrated HCl for about 34 hours on a steam bath. The product usually forms in a gelatinous layer which can be recovered by decanting the aqueous layer and dissolving the product (residue) in ethanol and evaporating the ethanol. For purification purposes it is advantageous to redissolve the product in hot Water maintained at a high pH (about pH of 10) and acidifying the alkaline solution with an acid (5 N HCl) to precipitate the product, pentadecylbenzylphosphonic acid.
Example 3 Disodium pentadecylbenzylphosphonate is prepared by dissolving the free acid obtained as in Example 2 in hot water (about 70 C.) maintained at a high pH (about 11 or 12) with NaOH and evaporating the aqueous solution to dryness at about 140 C.
Example 4 Into a suitable reaction vessel are charged about 302 parts of dodecylbenzylchloride and about 165 parts of tri-ethyl phosphite. The temperature is raised to about 140 C. for about 10 hours at which time the temperature is slowly raised to about 160 C. When the evolution of ethyl chloride has essentially stopped (about 4 hours later) the reaction product is distilled in a molecular still at about 155-165 C. to yield diethyl dodecylbenzylphosphonate.
Example 5 The ester of Example 4 is hydrolyzed with excess concentrated HCl for about 30 hours on a steam bath. The product layer is recovered in substantially the same manner as in Example 2 to yield dodecylbenzylphosphonic acid.
Exampleo Dipotassium dodecylbenzylphosphonate is prepared by dissolving the free acid obtained as in Example 5 in hot water (about 70 C.) maintained at a high pH (about 11 or 12) with KOH and evaporating the aqueous solution to dryness at about 140 C.
Other long chain aliphatic benzy-lhalides which can be reacted with tri-lower alkyl phosphites according to the procedures as illustrated by the foregoing examples to form compounds of the instant invention include tetradecyl-, decyloctyland hexy-lbenzylchloride; hexadecenyl-, octadecenyl-, tetradecenyl-, dodecenyl-, decenylbenzylchloride; octadecadienylbenzylchloride 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 such inorganic alkali metal salts, oxides and hydroxides as NaNO Na O, Na CO KOH, K 0, K C KNO LiOH, LiNO Li C0 and the like, ammonium compounds such as (NH CO NH OH, and the like, and amines such as ethyl amine, diethyl amine, propyl amine, ethanol amine, triethanol amine, propylene diamine, propanol amine, 2-ethylhexyl amine, and the like.
The acid and Water-soluble salt compounds of the present invention are useful in minor amounts (usually from about 0.01% to about by weight) in aqueous solutions as surface tension reducing agents and the acid compounds exhibit the highly desirable features of being good Wetting agents as well as exhibiting good foam stability which is advantageous in such uses as hard surface cleansing compositions, toothpaste compositions, and the like.
The ester compounds of the present invention are useful in minor amounts (usually from about 0.005% to 5% 4 by weight) in gasoline as gasoline de-icer additives and are useful with many organic solvents such as perchloroethylene in amounts from about 05% to 10% by Weight as dry-cleaning surfactants.
What is claimed is: 1. A compound having the formula OOX B OX
OOH
CHri
R on
wherein: R is selected from the class consisting of alkyl and alkenyl radicals containing from 6 to 20 carbon atoms.
3. A long chain aliphatic benzylphosphonate ester compound having the formula R OR wherein R is selected from the class consisting of alkyl and alkenyl groups containing from 6 to 20 carbon atoms and R is a lower alkyl group containing from 1 to 5 carbon atoms.
4. A salt compound of a long chain aliphatic benzylphosphonic acid, said salt having the formula CHri wherein: R is selected from the class consisting of alkyl and alkenyl groups containing from 6 to 20 carbon atoms and X is a cation selected from the group consisting of alkali metal, ammonium and low molecular weight alkyl amines, alkylene amines and alkanol amines containing not more than 2 amine groups.'
5. An alkylbenzylphosphonic compound having the formula oHPi R ox
wherein: R is an alkyl group containing from 8 to 18 carbon atoms and X is selected from the class consisting of hydrogen and cations selected from the group consistmg of alkali metal, ammonium, and low molecular weight alkyl amines, alkylene amines and alkanol amines-coutammg not more than 2 amine groups.
6. Alkylbenzylphosphonic acid having the formula fi/OH CH2-P wherein: R is an alkyl group containing from 8 to 18 carbon atoms.
7. A salt compound of alkylbenzylphosphonic acid, said salt having the formula 8. Pentadecylbenzylphosphonic acid.
9. Diethyl pentadecylbenzylphosphonate. 10. Disodium pentadecylbenzylphosphonate. 11. Diethyl dodecylbenzylphosphonate.
12. Dodecylbenzylphosphonic acid.
13. Disodium dodecylbenzylphosphonate.
References Cited UNITED STATES PATENTS 2,594,454 4/1952 Kosolapoff 260-961XR 2,765,279 10/1956 Nusslein 260500 CHARLES B. PARKER, Primary Examiner.
15 A. H. SUTTO, Assistant Examiner.
Priority Applications (1)
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US374255A US3363032A (en) | 1964-06-11 | 1964-06-11 | Long chain aliphatic benzylphosphonic acids, esters and salts |
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US374255A US3363032A (en) | 1964-06-11 | 1964-06-11 | Long chain aliphatic benzylphosphonic acids, esters and salts |
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US3363032A true US3363032A (en) | 1968-01-09 |
Family
ID=23475958
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US374255A Expired - Lifetime US3363032A (en) | 1964-06-11 | 1964-06-11 | Long chain aliphatic benzylphosphonic acids, esters and salts |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3742040A (en) * | 1969-07-28 | 1973-06-26 | Stauffer Chemical Co | Alkylammonium alkylphosphonamidates |
US3925456A (en) * | 1973-08-27 | 1975-12-09 | Henkel & Cie Gmbh | Cyclic aminophosphonic acids |
US4308197A (en) * | 1980-04-21 | 1981-12-29 | Mcdonnell Douglas Corporation | Fire resistant composites |
US5242908A (en) * | 1990-02-02 | 1993-09-07 | Hoechst Aktiengesellschaft | Use of benzylphosphonic acid derivatives for the treatment of diseases caused by viruses |
US5391816A (en) * | 1993-11-08 | 1995-02-21 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
US5532226A (en) * | 1991-07-18 | 1996-07-02 | Ortho Pharmaceutical Corporation | Trifluoromethybenzylphosphonates useful in treating osteoporosis |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2594454A (en) * | 1946-05-31 | 1952-04-29 | Monsanto Chemicals | Organic phosphorus acids and esters |
US2765279A (en) * | 1949-03-11 | 1956-10-02 | Metallgesellschaft Ag | Shaped mixture of soap and phosphonate |
-
1964
- 1964-06-11 US US374255A patent/US3363032A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2594454A (en) * | 1946-05-31 | 1952-04-29 | Monsanto Chemicals | Organic phosphorus acids and esters |
US2765279A (en) * | 1949-03-11 | 1956-10-02 | Metallgesellschaft Ag | Shaped mixture of soap and phosphonate |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3742040A (en) * | 1969-07-28 | 1973-06-26 | Stauffer Chemical Co | Alkylammonium alkylphosphonamidates |
US3925456A (en) * | 1973-08-27 | 1975-12-09 | Henkel & Cie Gmbh | Cyclic aminophosphonic acids |
US4308197A (en) * | 1980-04-21 | 1981-12-29 | Mcdonnell Douglas Corporation | Fire resistant composites |
US5242908A (en) * | 1990-02-02 | 1993-09-07 | Hoechst Aktiengesellschaft | Use of benzylphosphonic acid derivatives for the treatment of diseases caused by viruses |
US5532226A (en) * | 1991-07-18 | 1996-07-02 | Ortho Pharmaceutical Corporation | Trifluoromethybenzylphosphonates useful in treating osteoporosis |
US5391816A (en) * | 1993-11-08 | 1995-02-21 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
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