CA1167468A - 2,4,4'-trimethylpentyl, cyclohexylphosphinic acid and its preparation - Google Patents
2,4,4'-trimethylpentyl, cyclohexylphosphinic acid and its preparationInfo
- Publication number
- CA1167468A CA1167468A CA000384712A CA384712A CA1167468A CA 1167468 A CA1167468 A CA 1167468A CA 000384712 A CA000384712 A CA 000384712A CA 384712 A CA384712 A CA 384712A CA 1167468 A CA1167468 A CA 1167468A
- Authority
- CA
- Canada
- Prior art keywords
- trimethylpentyl
- acid
- cyclohexylphosphinic
- cyclohexylphosphinic acid
- mono
- 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
Links
Abstract
TITLE
2,4,4'-TRIMETHYLPENTYL, CYCLOHEXYLPHOSPHINIC ACID AND ITS
PREPARATION
ABSTRACT
Free Radical Addition of Mono 2,4,4'-trimethyl-pentylphosphine to cyclohexene followed by the oxidation of the 2,4,4'-trimethylpentyl, cyclohexylphosphine with two moles of hydrogen peroxide is employed to prepare 2,4,4'-trimethylpentyl, cyclohexylphosphinic acid. The 2,4,4'-trimethylpentyl, cyclohexylphosphinic acid is use-ful as a cobalt extractant.
2,4,4'-TRIMETHYLPENTYL, CYCLOHEXYLPHOSPHINIC ACID AND ITS
PREPARATION
ABSTRACT
Free Radical Addition of Mono 2,4,4'-trimethyl-pentylphosphine to cyclohexene followed by the oxidation of the 2,4,4'-trimethylpentyl, cyclohexylphosphine with two moles of hydrogen peroxide is employed to prepare 2,4,4'-trimethylpentyl, cyclohexylphosphinic acid. The 2,4,4'-trimethylpentyl, cyclohexylphosphinic acid is use-ful as a cobalt extractant.
Description
'7 28, ~3 The invention relates to 2,4,4'-trimethylpentyl, cyclohexylphosphinic aoid, i.e., CH3 c~3 I
CH3-C-CH2-cH-cH2 ~ \ OH
and a method for the production thereof which comprises free radical addition of mono 2,4,4'-trimethylpentylphosphine to cyclohexene followed by the oxidation of the 2,4,4'-trimeth-ylpentyl, eyclohexylphosphine with two moles of hydrogen peroxide. The end product, either as an acid or in its salt form, finds utility as a cobalt extractant and, more specif-ically, as a selec~ive extractant for cobalt (II) in aqueous cobalt (II) ~ bearing solutions contalning nickel (II).
In the preparatlon of this compound free radical initiators of the azobis type are preferred although others, such as the peroxides, may be used. Azobisobu-trylnitrile is the most preferred. The temperature range of the reaction is directly related to the half life of the initiator employed. For azobisbutrylnitrile the temperature rang~ should be about 40-110C, preferably 60 to 90C. The mole ratio of olefin to mono alkylphosphine can vary from 0.1 to 10 depending on the relative rates of formation of the di-and tri-alkylphosphines. Preferably the range is between 0.5 to 3~ ~
In the oxidation stage, the oxidation of the dia-lkylphosphine to the dialkylphosphine oxide is exothermic and takes place readily at 30-100, preEerably for this first oxidation step at 50-70C. To convert the dialkyl-phosphine oxide to the dialkylphosphine acid, the temper-ature should be increased to within 50 to 120C, preferably 80 to 100C. Higher temperatures tend to remove one alkyl group forming some monoalkylphosphonic acid. At lower tem-peratures the oxidation is rather slow and excessive reaction times may be required.
Whereas the exact scope of the instant invention is set forth in the appended claims, the following specific examples illustrate certain aspects of the present inven-tion, and, more particularly, point out methods of evaluating the same. However, the examples are set forth for illustra-tion only and are not to be construed as limitations on the present invention except as set forth in the appended claims.
All parts and percentages are by weight unless otherwise specified.
EX~MPLE 1 500 parts of 09.5% mono 2,4,4'trimethylpentylphos-phine is charged along with 482 parts of cyclohexene to a 1 gallon autoclave. 15 parts of azobisobutrylnitrile (VAZ0 64~) is added and the mixture quickly heated to 60C. The temperature is then slowly raised from 60C to 87C over a 5 1/2 hour period.
The product contained 39.36% cyclohexene, 22.70%
mono 2,4,4' trimethylpentylphosphine, 35.26% 2,4,4' tri-methylpentyl, cyclohexylphosphine, and 0.35~/O 2,4,4' tri-methylpentyl, dicyclohexylphosphine.
- A further 20 parts of azobisobutrylnitrile is added to the mixture. It is heated quickly to 60C and then slowly from 60C to 89 over a 6 1/2 hour period.
The product contained 34.39% cyclohexene,ll.l41 mono 2,4,4'trimethylpentylphosphine, 48.3% 2,4,4' tri-methylpentyl, cyclohexylphosphine, and 2.18% 2,4,4,' tri-methylpentyl dicyclohexylphosphine.
.~ .
,7 ~ ~ ( The product mix~ure is then distilled to remove the cyclohexene and mono 2,4,4'trimethylpentylphosphine. 516.~
of t.he residue containing 0.45% mono 2,4,4'trimethylpentyl-phosphine, 90.0% 2,4,4'trimethylpentyl cyclohexylphosphine and 3.48% 2,4,4' trimethylpentyl, dicyclohexylphosphine is placed in a stirred, heated resin flask under an inert atmosphere. The mixture is heated to 50C and 575 mL of 24%
H22 is added slowly with stirring over 1 1/2 hours. During ~hat time the temperature rose from 50C to 98C. To completely oxidize all the dialkylphosphine to the phos-phinic acid, an additional 500 g of 24% H22 is added and the mixture heated for a further 5 hours at 100C.
The product is then decanted as a vi~ous oil. It assayed 85.97Vlo phosphinic acid but also contained 9.58% mono
CH3-C-CH2-cH-cH2 ~ \ OH
and a method for the production thereof which comprises free radical addition of mono 2,4,4'-trimethylpentylphosphine to cyclohexene followed by the oxidation of the 2,4,4'-trimeth-ylpentyl, eyclohexylphosphine with two moles of hydrogen peroxide. The end product, either as an acid or in its salt form, finds utility as a cobalt extractant and, more specif-ically, as a selec~ive extractant for cobalt (II) in aqueous cobalt (II) ~ bearing solutions contalning nickel (II).
In the preparatlon of this compound free radical initiators of the azobis type are preferred although others, such as the peroxides, may be used. Azobisobu-trylnitrile is the most preferred. The temperature range of the reaction is directly related to the half life of the initiator employed. For azobisbutrylnitrile the temperature rang~ should be about 40-110C, preferably 60 to 90C. The mole ratio of olefin to mono alkylphosphine can vary from 0.1 to 10 depending on the relative rates of formation of the di-and tri-alkylphosphines. Preferably the range is between 0.5 to 3~ ~
In the oxidation stage, the oxidation of the dia-lkylphosphine to the dialkylphosphine oxide is exothermic and takes place readily at 30-100, preEerably for this first oxidation step at 50-70C. To convert the dialkyl-phosphine oxide to the dialkylphosphine acid, the temper-ature should be increased to within 50 to 120C, preferably 80 to 100C. Higher temperatures tend to remove one alkyl group forming some monoalkylphosphonic acid. At lower tem-peratures the oxidation is rather slow and excessive reaction times may be required.
Whereas the exact scope of the instant invention is set forth in the appended claims, the following specific examples illustrate certain aspects of the present inven-tion, and, more particularly, point out methods of evaluating the same. However, the examples are set forth for illustra-tion only and are not to be construed as limitations on the present invention except as set forth in the appended claims.
All parts and percentages are by weight unless otherwise specified.
EX~MPLE 1 500 parts of 09.5% mono 2,4,4'trimethylpentylphos-phine is charged along with 482 parts of cyclohexene to a 1 gallon autoclave. 15 parts of azobisobutrylnitrile (VAZ0 64~) is added and the mixture quickly heated to 60C. The temperature is then slowly raised from 60C to 87C over a 5 1/2 hour period.
The product contained 39.36% cyclohexene, 22.70%
mono 2,4,4' trimethylpentylphosphine, 35.26% 2,4,4' tri-methylpentyl, cyclohexylphosphine, and 0.35~/O 2,4,4' tri-methylpentyl, dicyclohexylphosphine.
- A further 20 parts of azobisobutrylnitrile is added to the mixture. It is heated quickly to 60C and then slowly from 60C to 89 over a 6 1/2 hour period.
The product contained 34.39% cyclohexene,ll.l41 mono 2,4,4'trimethylpentylphosphine, 48.3% 2,4,4' tri-methylpentyl, cyclohexylphosphine, and 2.18% 2,4,4,' tri-methylpentyl dicyclohexylphosphine.
.~ .
,7 ~ ~ ( The product mix~ure is then distilled to remove the cyclohexene and mono 2,4,4'trimethylpentylphosphine. 516.~
of t.he residue containing 0.45% mono 2,4,4'trimethylpentyl-phosphine, 90.0% 2,4,4'trimethylpentyl cyclohexylphosphine and 3.48% 2,4,4' trimethylpentyl, dicyclohexylphosphine is placed in a stirred, heated resin flask under an inert atmosphere. The mixture is heated to 50C and 575 mL of 24%
H22 is added slowly with stirring over 1 1/2 hours. During ~hat time the temperature rose from 50C to 98C. To completely oxidize all the dialkylphosphine to the phos-phinic acid, an additional 500 g of 24% H22 is added and the mixture heated for a further 5 hours at 100C.
The product is then decanted as a vi~ous oil. It assayed 85.97Vlo phosphinic acid but also contained 9.58% mono
2,4,4' trimethylpentylphosphonic acid. During the severe oxidation conditions, a portion of the cyclohexyl groups were removed and the resulting 2,4,4' trimethylpentylphosphine is oxidized to 2,4,4' trimethylpentylphosphonic acid.
Most oE the phosphonic acid is removed by scrubbing with 0.1N NaOH and water. The final product assayed 85.37%
2,4,4' trimethylpentyl, cyclohexylphosphinic acid and 4.86%
2,4,4' trimethylpentylphosphonic acid.
The product is a viscous oil and had a pKa of 6.04 in 75% isopropanol. The 31 p N~ chemical shift in toiuene is -53.13 ppm with respect to 85% H3PO4 EXA~LE 2 The following example illustrates the ability of 2,4,4' trimethylpentyl, cyclohexyl phosphinic acid to sep-arate cobalt (II) from nickel (II).
The 2,4,4'-trimethylpentyl, cyclohexylphosphinic acid is dissolved in an aliphatic petroleum diluent (Solvesso~ 100) modified with 5% v/v isoderanol to obtain a concentration of 15% by volume, then a predetermined amount of 28% ammonium hydroxide is added to adjust the pH. An aliquot (50 mls) is shaken at 50C. for 5 minutes at 50C with an equal volume oE an aqueous solution containing ~.05 gpl of cobalt (II) and 102.4 gpl oE nickel (II), respectively, as sulfate salts, to extract the cobalt (II) into the organic phase. The aqueous phase is then separated from the organic phase and analyzed for cobalt (II) content. Based on the results obtalned, the percent cobalt (II) extracted is cal-culated by mass balance. The percent nickel (II) extracted is determined by analyzing the organic phase. The results obtained are shown in Table I.
TABLE I
% Metal ExtractionCo/Ni Separation Equilibrium Co Ni Factor pH
85.1 0.78 726 4.70 95.6 1.66 1274 5.18 98.4 3.19 1910 5.53 99.9 4.64 21030 5.80 (1) Separation Factor = EA Co (II~, where EA Ni (II) equilibrium concentration of E =the metal in the or~anic phase A
equilibrium concentration of the metal in the aqueous phase
Most oE the phosphonic acid is removed by scrubbing with 0.1N NaOH and water. The final product assayed 85.37%
2,4,4' trimethylpentyl, cyclohexylphosphinic acid and 4.86%
2,4,4' trimethylpentylphosphonic acid.
The product is a viscous oil and had a pKa of 6.04 in 75% isopropanol. The 31 p N~ chemical shift in toiuene is -53.13 ppm with respect to 85% H3PO4 EXA~LE 2 The following example illustrates the ability of 2,4,4' trimethylpentyl, cyclohexyl phosphinic acid to sep-arate cobalt (II) from nickel (II).
The 2,4,4'-trimethylpentyl, cyclohexylphosphinic acid is dissolved in an aliphatic petroleum diluent (Solvesso~ 100) modified with 5% v/v isoderanol to obtain a concentration of 15% by volume, then a predetermined amount of 28% ammonium hydroxide is added to adjust the pH. An aliquot (50 mls) is shaken at 50C. for 5 minutes at 50C with an equal volume oE an aqueous solution containing ~.05 gpl of cobalt (II) and 102.4 gpl oE nickel (II), respectively, as sulfate salts, to extract the cobalt (II) into the organic phase. The aqueous phase is then separated from the organic phase and analyzed for cobalt (II) content. Based on the results obtalned, the percent cobalt (II) extracted is cal-culated by mass balance. The percent nickel (II) extracted is determined by analyzing the organic phase. The results obtained are shown in Table I.
TABLE I
% Metal ExtractionCo/Ni Separation Equilibrium Co Ni Factor pH
85.1 0.78 726 4.70 95.6 1.66 1274 5.18 98.4 3.19 1910 5.53 99.9 4.64 21030 5.80 (1) Separation Factor = EA Co (II~, where EA Ni (II) equilibrium concentration of E =the metal in the or~anic phase A
equilibrium concentration of the metal in the aqueous phase
Claims
1. The compound 2,4,4'-trimethylpentyl, cyclo-hexylpbosphinic acid.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18229680A | 1980-08-28 | 1980-08-28 | |
| US182,296 | 1980-08-28 | ||
| US06/263,459 US4321213A (en) | 1981-05-14 | 1981-05-14 | 2,4,4'-Trimethylpentyl, cyclohexylphosphinic acid and its preparation |
| US263,459 | 1988-10-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1167468A true CA1167468A (en) | 1984-05-15 |
Family
ID=26877967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000384712A Expired CA1167468A (en) | 1980-08-28 | 1981-08-27 | 2,4,4'-trimethylpentyl, cyclohexylphosphinic acid and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1167468A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544505A (en) * | 2015-09-16 | 2017-03-29 | 金发科技股份有限公司 | A kind of extractant composition and preparation method and application |
| CN110746455A (en) * | 2019-11-25 | 2020-02-04 | 岳阳富和科技有限公司 | Preparation method of aluminum bis (2, 4, 4-trimethylpentyl) phosphinate |
-
1981
- 1981-08-27 CA CA000384712A patent/CA1167468A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544505A (en) * | 2015-09-16 | 2017-03-29 | 金发科技股份有限公司 | A kind of extractant composition and preparation method and application |
| CN110746455A (en) * | 2019-11-25 | 2020-02-04 | 岳阳富和科技有限公司 | Preparation method of aluminum bis (2, 4, 4-trimethylpentyl) phosphinate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4374780A (en) | Di-2,4,4'-trimethylpentylphosphinic acid and its preparation | |
| Peterson | Phosphinomethyllithium compounds IV. An improved method of preparation and some synthetic applications | |
| JPS6227529A (en) | Method for selectively extracting metal from aqueous solution using dithiophosphinic acid | |
| Osseo-Asare et al. | Synergic extraction of nickel and cobalt by LIX63-dinonylnaphthalene sulfonic acid mixtures | |
| US4595779A (en) | Stable lithium diisopropylamide and method of preparation | |
| EP0236542B1 (en) | Novel organic phosphinic acid compounds | |
| EP0400311B1 (en) | Metal recovery with monothiophosphinic acids | |
| RU2451021C2 (en) | Novel phosphinic acids and sulphur-containing derivatives thereof, and synthesis methods thereof | |
| CA1167468A (en) | 2,4,4'-trimethylpentyl, cyclohexylphosphinic acid and its preparation | |
| US4321213A (en) | 2,4,4'-Trimethylpentyl, cyclohexylphosphinic acid and its preparation | |
| AU601243B2 (en) | Gallium complexes and solvent extraction of gallium | |
| US4906764A (en) | Process for producing phosphinylamino acid derivatives | |
| US3102900A (en) | Alkyl phosphonate esters and process for preparing same | |
| Ossola et al. | Organometallic amides of uranium (IV) and thorium (IV) involving one, two, or three cyclopentadienyl ligands | |
| CA1176272A (en) | 2,4,4'-trimethylpentylphosphinic acid and its preparation | |
| CA2077601A1 (en) | Recovery of indium by solvent extraction using trialkyl-phosphine oxides | |
| US4778663A (en) | Uranium recovery from wet process phosphoric acid unsymmetrical phosphine oxides | |
| US4555368A (en) | Process for synthesizing diorganomonothiophosphinates | |
| SU1701632A1 (en) | Method of producing rubidium complexes of difluorides of 3d-transient metals | |
| US4133869A (en) | Hydrogen peroxide stabilization | |
| US4943646A (en) | Gallium complexes and solvent extraction of gallium | |
| US2945882A (en) | Method of preparing n, n', n''-triphenyl-borazole | |
| CA1179151A (en) | Extraction process for the selective romoval of cobalt (ii) from aqueous solutions | |
| US4425306A (en) | Method for the recovery of uranium from wet-process phosphoric acid | |
| US4083897A (en) | Process for preparing n-alkylated aminoalkylphosphonates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |