KR20030093282A - Phosphonium phosphinate compounds and their preparation - Google Patents

Abstract

Novel phosphonium phosphinate compounds and their preparation are disclosed. Phosphonium salts are ionic liquids, which are useful as polar solvents. The novel phosphonium phosphinate compounds are those represented by formula (I):

Formula I

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each hydrogen or substituted or unsubstituted hydrocarbyl; Y ₁ is O or S; Y ₂ is O or S.

Description

Phosphonium phosphinate compound and its preparation {PHOSPHONIUM PHOSPHINATE COMPOUNDS AND THEIR PREPARATION}

Low melting or liquid phosphonium salts have been found to be useful as polar solvents known as "ion liquids". Ionic liquids have the potential to be used in place of conventional organic solvents for chemical reactions in many respects. For industrial purposes, the low vapor pressure of ionic liquids is a very important feature. Such ionic liquids are virtually nonvolatile, which is a property that solves many of the problems involved that are typical of conventional organic solvents. Ionic liquids are often composed of weakly coordinating ions and have the potential to provide solvents with high polarity but weak coordination. Moreover, most of these solvents are incompatible with conventional organic solvents, providing a non-aqueous polar system instead of a biphasic system. Due to the unique nature of these solvents, unique combinations of reagents can be used to ensure they are in the same phase. A recent review of the nature and use of ionic liquids is presented in the paper "Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis," by Thomas Welton (Chem. Rev. 1999, 99, 2071-2083). have.

Ionic liquids provide solvents with a wide range of liquids and a high degree of thermal stability. However, there remains a need to develop new ionic liquids with unique physical and chemical properties to increase the choice of solvents available to chemists.

1 shows the results of TGA analysis of trihexyl (tetradecyl) phosphonium bis (2,4,4'-trimethylpentyl) phosphinate.

Figure 2 shows the results of TGA analysis of trihexyl (tetradecyl) phosphonium diisobutyl phosphinate.

3 is a ³¹ P NMR spectrum of trihexyl (tetradecyl) phosphonium dicyclohexylphosphinate.

4 shows the results of a thermogravimetric analysis (TGA) of trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate.

5 is a ³¹ P NMR spectrum of trihexyl (tetradecyl) phosphonium diisobutyldithiophosphinate.

FIG. 6 shows the results of TGA analysis of trihexyl (tetradecyl) phosphonium diisobutyldithiophosphinate.

Description of Preferred Embodiments

The present invention relates to compounds of formula I as described above, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each hydrogen or a hydrocarbyl group; Y ₁ is O or S; Y ₂ is O or S). It is possible for the R ₁ to R ₆ groups to have substituents or to include heteroatoms, provided that the substituents or heteroatoms do not interfere with the preparation of the compounds according to the invention and do not adversely affect the desired properties of the compounds. Acceptable substituents include alkoxy, alkylthio, acetyl and hydroxy groups, and acceptable heteroatoms include oxygen and sulfur. Substituents have the potential to increase the compound cost of the present invention, and when the compound is often used as a solvent, it is used in such a volume that the cost becomes an important factor. Therefore, most substituents are considered to be absent.

Preferably, each R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, and 2 to 30 carbon atoms Alkenyl groups, alkynyl groups having 2 to 30 carbon atoms, aryl groups or aralkyl groups having 6 to 18 carbon atoms.

Alkyl groups with more than 18 carbon atoms, especially those with more than 20 carbon atoms, are likely to increase costs. Since cost is an important factor in solvent production, in practical terms alkyl groups should generally be considered to have no more than 20 carbon atoms. Accordingly, more preferred are compounds according to formula (I), wherein each R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently alkyl groups having 5 to 20 carbon atoms. For example, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are n-butyl, isobutyl, n-pentyl, cyclopentyl, isopentyl, n-hexyl, cyclohexyl, (2,4 , 4'-trimethyl) pentyl, cyclooctyl, tetradecyl and the like. However, at least one of R ₁ to R ₄ preferably contains more carbon atoms, for example 14 or more. In most cases, it is preferable that R ₁ to R ₄ are not the same. In most aspects, at least one of R ₁ to R ₄ are preferably a number of carbon atoms containing from significant than the remaining R ₁ to R _4. Compounds in which R ₁ to R ₄ are not the same are called asymmetric.

In most applications, it is preferred that Y ₁ and Y ₂ are both O. For example, in chemical reactions using certain metal catalysts, such as Pd (OAc) ₂ , it is preferred that both Y ₁ and Y ₂ be O because thio groups present in the phosphinate anion may interfere with the action of the catalyst. . The phosphonium thiophosphinate compound is useful as a solvent for chemical reactions containing no metal catalyst.

Preferred compounds are those according to formula I, wherein each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is independently an aryl group or a substituted aryl group. For example, one or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be phenyl, phenethyl, xylyl or naphthyl.

In some applications compounds according to formula (I) that are hydrophobic or "water immiscible" are preferred. The term "water immiscible" refers to a compound which forms a two-phase system when mixed with water, but does not exclude an ionic liquid that dissolves in water or an ionic liquid that dissolves water if only two-phase systems are formed. Thus, compounds having a high total carbon number, such as compounds having 20 or more, in particular more than 25 or 26, or compounds having at least one aryl group are preferred because of their higher hydrophobicity. Water immiscibility is a desirable feature of phosphinium phosphinates because it not only provides compounds useful for causing two-phase reactions with aqueous phases, but also facilitates the purification and separation of phosphonium phosphinates when prepared according to certain methods. . There is no absolute upper limit to the total number of carbon atoms that may be present in R ₁ to R ₆ . However, it is not desirable that the total carbon atoms exceed 50.

For most purposes, materials that are liquid at room temperature are very desirable. Thus, preferred compounds are those in which certain R ₁ to R ₆ groups are selected to yield compounds that are liquid at room temperature. The choice of specific R ₁ to R ₆ groups to achieve specific melting points and water immiscibility can be made within the ability of those skilled in the art, although some routine experimentation may be required. For example, the asymmetry and branching of the hydrocarbyl groups R ₁ to R ₆ of the phosphonium cation or the phosphinate anion are important determinants of the melting point: the melting point tends to decrease with increasing asymmetry and branching. Branching may occur at alpha or omega carbons or at any intermediate point. The increase in the total number of carbon atoms present in the hydrocarbyl groups R ₁ to R ₆ tends to increase the melting point, which can be offset somewhat by asymmetry and branching. For example, the properties of a compound in which the phosphonium cation contains four decyl groups as R ₁ to R ₄ are the properties of the compound having three undecyl groups and one heptyl group, even though the total carbon atoms of the two cations are 40 And differ from each other.

For some purposes, compounds according to formula (I) with chirality may be particularly preferred because they further provide a chiral environment for chemical reactions. Examples include compounds in which one of R ₁ to R ₆ is an enantiomer of 2,4,4'-trimethylpentyl having one chiral atom.

Examples of preferred compounds according to formula (I) include the following:

R ₁ , R ₂ and R ₃ are each n-hexyl and R ₄ is n-tetradecyl,

R ₅ and R ₆ are 2,4,4'-trimethylpentyl and Y ₁ and Y ₂ are O; or

R ₅ and R ₆ are isobutyl and Y ₁ and Y ₂ are O; or

R ₅ and R ₆ are cyclohexyl and Y ₁ and Y ₂ are O; or

R ₅ and R ₆ are isobutyl and Y ₁ and Y ₂ are S.

The present invention also provides a method for preparing a phosphonium phosphinate compound according to formula (I). In general, phosphonium phosphinates can be prepared by reacting the phosphonium salt of formula II with 1) phosphinic acid and base of formula III, or 2) phosphinate salt of formula IV. Alternatively, phosphonium phosphinate can be prepared by reacting phosphonium hydroxide of formula II with phosphinic acid. The reaction temperature is not critical but is conveniently carried out at elevated temperatures, up to about 100 ° C., preferably in the range from 45 to 70 ° C. Higher temperatures make phase separation easier.

If the phosphonium phosphinate is immiscible with water, the phosphonium salt of formula (II) can be prepared by first mixing with the phosphinic acid compound of formula (III) and water under stirring or other means of mixing, and then adding a base. The mixture is further stirred. Stopping the mixing will separate the reaction mixture into an organic phase and an aqueous phase containing the phosphonium phosphinate product. The aqueous phase can be decanted and the organic phase can then be washed with water to remove salt by-products (e.g. sodium chloride) formed in the reaction. If necessary, the residue can be removed from the organic layer, for example by vacuum stripping.

As a variant of the method described above, first a phosphonium salt and water are mixed, then sodium hydroxide is added and finally phosphinic acid is added. Stopping the mixing will separate the reaction mixture into an organic phase and an aqueous phase that can be further treated as described in the process above.

Phosphonium phosphinates according to formula I, which are immiscible with water, can be prepared by mixing the phosphonium salts of formula II with the phosphinate salts of formula IV and water under stirring. The mixture is further stirred, i.e. for 1 h. Stopping mixing will separate the reaction mixture into an aqueous layer and an organic layer. The aqueous layer may be in accordance with still, the organic layer left an arbitrary [M ^+] [X ^-], which is water can be cleaned several times to remove the _k. If necessary, the dissolved water can be removed from the organic layer by vacuum peeling or the like.

Another preferred method can be used to prepare phosphonium phosphinates that are miscible or immiscible with water. The phosphonium phosphinate according to formula (I) can be prepared by reacting a phosphonium hydroxide of formula (II), i.e. a compound of formula (II) wherein X ^- is OH ^- with phosphinic acid of formula (III) to obtain phosphonium phosphinate and water have. The water obtained by this acid-base reaction can be removed, for example, by vacuum stripping. Since the phosphonium phosphinate obtained in this way does not require water washing for salt removal, It can be used to prepare miscible or immiscible phosphonium phosphinates. This method is preferred for producing phosphonium phosphinates having a small total carbon atoms, that is, on the order of 7 to 10 carbons.

It should be noted that the compounds of formula (I) contain up to six hydrocarbyl groups R ₁ to R ₆ . The specific properties of the compounds represented by the formula (I) depend on the values provided by these six groups. Therefore, by selecting these groups differently, the properties of the compounds of the present invention can be finely adjusted. Accordingly, the compounds of the present invention can be designed as compounds which are liquid at certain temperatures and are water immiscible. Changes in one or more of the R ₁ through R ₆ groups can affect changes in this property. The presence of six groups for this purpose is advantageous when compared to known ionic liquids based on dialkylimidazolium cations with only two groups that can be changed.

Most of the compounds of the present invention have a density of less than one. In conclusion, the two-phase system with water forms an upper layer. In this respect, the compounds of the present invention differ from known ionic liquids based on dialkyl imidazolium cations that have a density greater than 1 and tend to form an underlayer in a two-phase system with water.

The phosphonium phosphinate salts of the present invention can be used as polar solvents. In a preferred embodiment, the phosphonium phosphinate of the present invention is a chemical reaction such as Michael addition reaction, aryl coupling reaction, Diels Alder reaction, alkylation reaction, two-phase catalysis, Heck reaction, hydrogenation reaction It can be used as a polar solvent of enzyme reactions such as lipase reaction.

Through the following examples (see Examples 5 and 6), it can be seen that the phosphonium phosphinate of the present invention is a suitable solvent for the synthesis of biphenyl through homocoupling of bromobenzene or iodobenzene. Biaryls are very important in synthetic organic chemistry because they have many industrial and pharmacological uses that have been identified. The precision of liquid crystals often depends on, for example, the synthesis of the biaryl backbone. Among natural products, biophenomycin and steganacin have this biaryl molecular infrastructure. Therefore, their production in a cost effective manner is particularly important. Biaryl's Ullman synthesis generally requires high temperature conditions (200 ° C.) and requires an equivalent molar amount of copper. This stoichiometric amount of metal and the need for high temperatures can be eliminated through the use of a palladium catalyst and a suitable ionic solvent such as the phosphonium phosphinate of the present invention.

In Example 8, the suitability of phosphonium phosphinate as a solvent for carbonylation with a palladium catalyst is demonstrated. Carbonylation of aryl-X derivatives with palladium catalysts constitutes a powerful method of C-C coupling reactions useful for the synthesis of various aromatic carboxylate acid derivatives such as amides and esters. The aryl palladium species formed as intermediates undergo a nucleophilic attack of alcohols, water and amines after an easy CO insertion reaction to give acids, esters and amides, respectively. This reaction can be carried out using an aryl halide with carbon monoxide and nucleophiles in the presence of a catalytic amount of palladium compound. In addition, other metal catalysts derived from Co and Ni have also been used as catalysts.

As can be seen from the following examples, some examples according to the invention and some examples for comparison yield different yields depending on the solvent selected for the various reactions. The phosphonium phosphinate of the present invention provides good or best results in many of the following examples. Thus, the phosphonium phosphinate of the present invention provides a significant improvement of the synthetic method.

The present invention provides a novel phosphonium phosphinate compound and a process for preparing the compound. The phosphonium phosphinate compounds can have various phosphonium cations and various phosphinate and dithiophosphinate anions.

The new phosphonium phosphinate is represented by the formula (I):

Formula I

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each hydrogen atoms or hydrocarbyl groups, provided that no more than two of R ₁ to R _{4 and} one or less of R ₅ and R ₆ Is hydrogen;

Y ₁ is O or S;

Y ₂ is O or S.

Preferably each of R ₁ to R ₆ is a hydrocarbyl group.

In still another aspect, the present invention is a method for producing a phosphonium phosphinate compound represented by the above formula (I),

i) reacting a compound represented by formula (ii) with ii) a compound represented by formula (IV):

Formula II

Formula IV

Wherein R ₁ to R ₄ are as described above,

X ^- is the leaving group,

R ₅ , R ₆ , Y ₁ and Y ₂ are as defined in Formula I above,

M ^{k +} is H ⁺ or a metal cation having a valence of "k".

Preferably, when M ^{k +} is H ⁺ and X ⁻ is a leaving group other than OH ⁻ , the reaction is preferably carried out in the presence of a base. If X ⁻ is OH ⁻ and M ^{k +} is H ^+, no base is required. If M ^{k +} is a metal cation having a valence of “k”, X ⁻ is a leaving group other than OH ⁻ .

Thus, in one embodiment, the compound represented by formula (I) reacts i) a compound represented by formula (II) with ii) a compound represented by formula (III), wherein X ⁻ in formula (II) is any leaving other than OH ⁻ In the case of a group, it may be prepared by reacting with a base, such as a carbonate or hydroxide of an alkali or alkaline earth metal:

Formula II

Formula III

In the above formulas,

R ₁ to R ₄ are the same as described above in Chemical Formula I,

X ⁻ is a leaving group such as hydroxide (OH ⁻ ), acetate, sulfate or halide, preferably chloride, bromide or iodide,

R ₅ , R ₆ , Y ₁ and Y ₂ are as described above in Chemical Formula (I).

As another embodiment, the compound represented by the formula (I) may also be prepared by reacting the compound represented by the formula (II) described above with ii) a compound represented by the following formula (IV):

Formula IV

In this formula, R ₅ , R ₆ , Y ₁ and Y ₂ are as described above in the formula (I),

M ^{k +} is ammonium or metal and k is the valence of the metal. Suitable metals are all metals which form water-soluble salts with anions, such as alkali metals, preferably Na ⁺ or K ⁺ .

As another embodiment of the present invention, the compound represented by the formula (I) is useful as an ionic solvent.

The foregoing has outlined the nature of the present invention, and preferred embodiments will now be described in detail with reference to the accompanying drawings in which:

Example 1:

Trihexyl (tetradecyl) phosphonium bis (2,4,4'-trimethylpentyl) phosphinate

Trihexyl (tetradecyl) phosphonium bis (2,4,4'-trimethylpentyl) phosphinate was prepared according to the following method. The following compound was added to a 5 liter reactor stirred and jacketed:

1.880 mol of trihexyl (tetradecyl) phosphonium chloride (1003 g of CYPHOS 3653 containing 97.2% trihexyl (tetradecyl) phosphonium chloride)

1.875 mol of bis (2,4,4'-trimethylpentyl) phosphinic acid (625 g of CYANEX 272 containing 87% bis (2,4,4'-trimethylpentyl) phosphinic acid) and

1369 g of water.

After the mixture was heated to 54 ° C., 25% aqueous sodium hydroxide solution (82.3 g of 97% sodium hydroxide (2 mol), 236.8 g of water) was added for about 32 minutes. The two phases were further stirred at 55 ° C. for 1/2 hour.

Agitation was then stopped and the reaction mixture was separated into a two phase system consisting of an upper organic phase and a lower aqueous phase (phase separation took about 2 minutes). The lower aqueous phase was decanted and the upper organic layer was stirred three times with about 1300 g of distilled water per wash by stirring at 55 ° C. for 1 hour. The time required for bulk phase separation was increased for each successive wash as follows: 2 minutes, 30 minutes, then 8 minutes for bulk phase separation for the final wash, but 22 hours for the organic layer to become clear. It became.

After washing and phase separation, vacuum removal was performed to remove dissolved water from the organic layer. About 230 g of water (13.2 wt%) was removed after vacuum exfoliation at 125 ° C. under 4 mm HG pressure. The final organic layer became completely transparent.

result

The aqueous phase was analyzed for chloride ions (see Table 1). In the primary isolate, 82.9% of chloride ions were removed. The primary, secondary and tertiary washes further removed 12.0%, 1.7% and 0.2% of chloride ions, respectively, resulting in a total of 96.7%.

TGA analysis of trihexyl (tetradecyl) phosphonium bis (2,4,4'-trimethylpentyl) phosphinate samples revealed thermal stability up to about 300 ° C. (see FIG. 1). This analysis also suggested that the product may contain as much as 4-6% moisture.

Table 1

Preparation of Trihexyl (tetradecyl) phosphonium bis (2,4,4'-trimethylpentyl) phosphinate

Bis (2,4,4'-trimethylpentyl) phosphinic acid (CYANEX 272) 87.0% R " ₂ P (O) OH R "= bis 2,4,4'-trimethylpentyl CYPHOS 3653 97.2% R ₃ R'PCl 2.1% R ₃ PCl0.2% HCl R = n-butylR '= n-tetradecyl

Chloride Residue Weight (g) mole Cl% Cl mol Cl removal rate (%) CYANEX 272 625 1.875 0.000 CYPHOS 3653 1003 1.880 1.946 97% NaOH 82.3 1.996 0.000 water 1605 Primary isolate 1404 4.0720 1.613 82.9 Secondary separation 1283 0.6450 0.233 12.0 Tertiary isolate 1305 0.0873 0.032 1.7 Quaternary isolate 1303 0.0096 0.004 0.2 total 1.882 96.7

Example 2: Trihexyl (tetradecyl) phosphonium diisobutyl phosphinate

Trihexyl (tetradecyl) phosphonium diisobutyl phosphinate was prepared according to the following method. The following components were added to a stirred and jacketed 5 liter reactor:

Trihexyl (tetradecyl) phosphonium chloride 2.004 mol (CYPHOS 3653 1069 g)

2.004 mol (91.3% diisobutyl phosphinic acid 390.8 g) diisobutylphosphinic acid and

1114 g of water.

After the mixture was heated to 55 ° C., 25% aqueous sodium hydroxide solution (87.7 g of 97% sodium hydroxide (2 mol), 240 g of water) was added for 30 minutes. The two phases were further stirred at 55 ° C. for 1 hour.

Agitation was then stopped and the reaction mixture was separated into a two phase system consisting of an upper organic phase and a lower aqueous phase (phase separation took about 2 minutes). The lower aqueous phase was decanted and the upper organic layer was stirred three times with about 1300 g of distilled water per wash by stirring at 55 ° C. for 1 hour. The time required for bulk phase separation was increased with each successive wash. After washing, the organic and liquid phases were initially cloudy but left clear overnight and became clear.

After washing the phases were completely separated and then vacuumed off to remove dissolved water from the organic layer. About 13.4% by weight of water was removed after vacuum exfoliation at 135 ° C. under 4 mmHG pressure. The final organic layer became completely transparent.

result

The separated aqueous phase was analyzed for chloride ions (see Table 2). In the primary isolate, 63.7% of chloride ions were removed. The primary, secondary and tertiary washes further removed 5.3%, 0.3% and 0.2% of chloride ions, respectively, for a total of 69.5%.

TGA analysis of the trihexyl (tetradecyl) phosphonium diisobutyl phosphinate sample was confirmed to have thermal stability up to about 300 ℃ (see Figure 2). This analysis also suggested that the product may contain as much as 4-6% moisture.

TABLE 2

Preparation of Trihexyl (tetradecyl) phosphonium diisobutylphosphinate

Diisobutylphosphinic acid 91.3% R " ₂ P (O) OH R "= Isobutyl CYPHOS 3653 97.2% R ₃ R'PCl 2.1% R ₃ PCl0.2% HCl R = n-butylR '= n-tetradecyl

Chloride Residue Weight (g) mole Cl% Cl mol Cl removal rate (%) R " ₂ P (O) OH 390.8 2.004 0.000 CYPHOS 3653 1069 2.004 2.074 97% NaOH 87.7 2.127 0.000 water 1354 Primary isolate 1245 3.7610 1.321 63.7 Secondary separation 1278 0.3051 0.110 5.3 Tertiary isolate 1270 0.0174 0.006 0.3 Quaternary isolate 1300 0.0090 0.003 0.2 total 1.440 69.5

Example 3: Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate

Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate was prepared according to the following method. The following components were added to the stirred and jacketed reactor:

Trihexyl (tetradecyl) phosphonium chloride 1.907 mol (CYPHOS 3653 1017 g)

1.909 mol (349 g dicyclohexyl phosphinate, 2.417 mol) dicyclohexyl phosphinate and

1200 g of water.

After the mixture was heated to 55 ° C., 25% aqueous sodium hydroxide solution (83.4 g (2.022 mol) of sodium hydroxide, 210 g of water) was added for 30 minutes. The two phases were further stirred at 55 ° C. for 1 hour.

Agitation was then stopped and the reaction mixture was separated into a two phase system consisting of an upper organic phase and a lower aqueous phase (phase separation took about 4 minutes). The lower aqueous phase was decanted and the upper organic layer was washed three times with 1300 g of distilled water with stirring.

After washing the phases were separated and then vacuum stripped to remove dissolved water from the organic layer. About 210 g of water (14 wt% water) was removed after vacuum exfoliation at 138 ° C. under 4 mm HG pressure. The final organic layer became completely transparent.

result

The separated aqueous phase was analyzed for chloride ions. 82.2% of chloride ions were removed from the primary isolate, and 14.7%, 1.7% and 0.2% of chloride ions were further removed from the primary, secondary and tertiary washes, removing a total of 98.8% (see Table 3). ).

The organic layer sample was analyzed by ³¹ P NMR (FIG. 3). This NMR spectrum shows two unique signals, +33.46 ppm for phosphonium cations and +31.2741 ppm for phosphinate anions, consistent with the reaction product trihexyl (tetradecyl) phosphonium dicyclohexylphosphinate. Indicated.

TGA analysis of the trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate sample was found to be thermally stable up to about 300 ℃ (see Figure 4). This analysis also suggested that the product may contain as much as 7-8% moisture.

TABLE 3

Preparation of trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate

Dicyclohexylphosphinic acid 98.0% R " ₂ P (O) OH R "= cyclohexyl CYPHOS 3653 97.2% R ₃ R'PCl R = n-butylR '= n-tetradecyl

Chloride Residue Weight (g) mole Cl% Cl mol Cl removal rate (%) R " ₂ P (O) OH 439 1.909 0.000 CYPHOS 3653 1017 1.907 1.973 97% NaOH 83.4 2.022 0.000 water 1200 Primary isolate 1249 4.6040 1.622 82.2 Secondary separation 1344 0.7650 0.290 14.7 Tertiary isolate 1300 0.0898 0.033 1.7 Quaternary isolate 1310 0.0090 0.003 0.2 total 1.948 98.8

Table 4

Peeling Water from Phosphonium Phosphate (R ₃ R'PR "P (O) O)

R " % Water removed Temperature (℃) Pressure (mmHg) 2,4,4'-trimethylpentyl 13.2 125 4 Isobutyl 13.4 135 4 Cyclohexyl 14.0 138 4

Example 4: Trihexyl (tetradecyl) phosphonium diisobutyl dithiophosphinate

Trihexyl (tetradecyl) phosphonium diisobutyl dithiophosphinate was prepared according to the following method. The following components were added to the stirred and jacketed reactor:

Trihexyl (tetradecyl) phosphonium chloride 1.91 mol (CYPHOS 3653, 1019 g)

1.99 mol of sodium diisobutyldithiophosphinate (925 g of AEROPHINE 3418A, 50% aqueous solution of sodium diisobutyldithiophosphinate), and

1500 g of water.

The mixture was heated to 50 ° C. and then stirred for 30 minutes. Agitation was stopped and the reaction mixture was separated into a two phase system consisting of an upper organic phase and a lower aqueous phase (phase separation took about 4 minutes). The lower aqueous phase was decanted and the upper organic layer was washed three times with 1400 g of 50 ° C. distilled water with stirring.

The organic layer was vacuum peeled at 125 ° C. under 1.2 mm HG pressure. Only 25 g of water was removed. The final organic layer became completely transparent.

result

The final product was a liquid at room temperature. The chloride content was 0.0099%.

^{The 31} P NMR spectrum showed two unique signals: +33.37 ppm, phosphonium cation and +65.81 ppm, dithiophosphinate anion (FIG. 5).

TGA analysis of the trihexyl (tetradecyl) phosphonium diisobutyldithiophosphinate sample was confirmed to be thermally stable up to about 270 ℃ (see Figure 6). The analysis also suggested that the product contained about 0.5% water.

Example 5: Pd (OAc) in Various Phosphonium Ion Liquids ₂ Synthesis of Biphenyls by Homogeneous Coupling of Bromobenzene Using

Homocoupling of bromobenzene was performed in a variety of phosphonium ionic liquids as a series of experiments. The reaction proceeds as follows:

In the next experiment, the following components were added to the stirred and jacketed reactor:

Bromobenzene 1.0 g

2.0 g of isopropyl alcohol

K ₂ CO ₃ 1.5g

Pd (OAc) ₂ 0.03 g

These reagents were heated for 16 hours at 120 ° C. in a phosphonium ion liquid solvent selected from the following groups:

Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate;

Trihexyl (tetradecyl) phosphonium decanoate;

Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate;

Trihexyl (tetradecyl) phosphonium tripleamide; And

Trihexyl (tetradecyl) phosphonium triflate.

The reaction mixture was cooled, poured into 50 ml of water and the total reaction mixture was extracted with petroleum ether (45-60 ° C.). The ionic liquid formed a recoverable intermediate layer. The petroleum ether layer was washed with water and then brine and concentrated. The residue was distilled off to give the required biaryl compound.

The total yield of biphenyl obtained using different solvents was measured and shown in Table 5. Yields of biphenyls were significantly different depending on the solvent selected. However, in two experiments in which phosphonium phosphinate compounds were used as solvents, a comparatively higher yield was shown in comparative experiments in which phosphonium triamide or triflate was used as solvent, thereby yielding Pd (OAc) ₂ . It was confirmed that the compound of the present invention is suitable for synthesizing biphenyl through homocoupling of bromobenzene. The reaction conditions were not optimized for every particular solvent, so the total yield is expected to be naturally improved.

Table 5

Synthesis of Biphenyls through Homo-Coupling of Bromobenzene Using Pd (OAc) ₂ in Various Phosphonium Ion Liquids

Experiment number Ionic liquid yield% One Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate 61 2 Trihexyl (tetradecyl) phosphonium decanoate 100 3 Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate 52 4 Trihexyl (tetradecyl) phosphonium tripleamide 26 5 Trihexyl (tetradecyl) phosphonium triflate 9

Example 6: Pd (OAc) as Catalyst ₂ Synthesis of Biphenyls through Homocoupling of Iodobenzene in Various Ionic Liquids

The reaction was carried out similarly to the reaction set forth in Example 5, except that iodobenzene was used as starting material.

The following components were added to the stirred and jacketed reactor:

Iodobenzene 1.0g

1.5 g of isopropyl alcohol

K ₂ CO ₃ 1.5g

Pd (OAc) ₂ 0.03 g

These reagents were heated for 18 hours at 120 ° C. in a phosphonium ion liquid solvent selected from the following groups:

Trihexyl (tetradecyl) phosphonium chloride;

Trihexyl (tetradecyl) phosphonium triflate;

Trihexyl (tetradecyl) phosphonium tripleamide;

Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate;

Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate;

Trihexyl (tetradecyl) phosphonium diisobutylphosphinate;

Trihexyl (tetradecyl) phosphonium decanoate;

Trihexyl (tetradecyl) phosphonium tetrafluoroborate; And

Trihexyl (tetradecyl) phosphonium hexafluorophosphate.

The total yield of biphenyls synthesized using different solvents was evaluated and presented in Table 6. The yield of biphenyls varied considerably depending on the solvent selected. The use of trihexyl (tetradecyl) phosphonium chloride as solvent was particularly low in biphenyl yield, since chloride ions interfered with the Pd (OAc) ₂ catalyst. When the phosphonium phosphinate compound according to the present invention was used as a solvent, the reaction proceeded in a high yield of about 100%. These results confirm that the phosphonium phosphinate compound does not interfere with the Pd (OAc) ₂ catalyst, making it a suitable solvent for biphenyl synthesis via homocoupling of iodobenzene using Pd (OAc) ₂ as a catalyst. Could.

Table 6

Homogeneous Coupling of Iodobenzene in Various Ionic Liquids Using Pd (OAc) ₂ Catalyst

Experiment number Ionic liquid % Conversion One Trihexyl (tetradecyl) phosphonium chloride 13 2 Trihexyl (tetradecyl) phosphonium triflate 100 3 Trihexyl (tetradecyl) phosphonium tripleamide 72 4 Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate 78 5 Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate 100 6 Trihexyl (tetradecyl) phosphonium diisobutyl phosphinate 100 7 Trihexyl (tetradecyl) phosphonium decanoate 100 8 Trihexyl (tetradecyl) phosphonium tetrafluoroborate 56 9 Trihexyl (tetradecyl) phosphonium hexafluorophosphate 50

Example 7: Pd (OAc) ₂ Hex-Coupling Reaction of Iodobenzene and Methylacrylate in Various Ionic Liquids Using Catalyst

The following components were added to the stirred and jacketed reactor:

Iodobenzene 1.0g

Methylacrylate 0.86g

K ₂ CO ₃ 2.0g

Pd (OAc) ₂ 0.05 g

The reaction mixture was heated at 80 ° C. for 14 hours in 2.0 g of phosphonium ion liquid solvent selected from the following group:

Trihexyl (tetradecyl) phosphonium chloride;

Trihexyl (tetradecyl) phosphonium triflate;

Trihexyl (tetradecyl) phosphonium tripleamide;

Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate;

Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate;

Trihexyl (tetradecyl) phosphonium diisobutylphosphinate;

Trihexyl (tetradecyl) phosphonium decanoate;

Trihexyl (tetradecyl) phosphonium tetrafluoroborate; And

Trihexyl (tetradecyl) phosphonium hexafluorophosphate.

The total yield is shown in Table 7. Reaction yields vary considerably depending on the solvent selected. A yield of about 100% was obtained when the three phosphonium phosphinate solvents of the present invention were used, and it was confirmed that the phosphonium phosphinate compound was a suitable solvent for the heck coupling reaction.

Similar series of experiments were conducted using ethylacrylate instead of methylacrylate. The results of this experiment are shown in Table 8. In general, the hex coupling reaction of iodobenzene and ethylacrylate provided a lower yield than the coupling reaction of iodobenzene and methylacrylate. However, it is clear from this experiment that the phosphonium phosphinate compound of the present invention is a suitable solvent for the heck coupling reaction.

TABLE 7

Hex-Coupling Reaction of Iodobenzene and Methylacrylate in Various Ionic Liquids Using Pd (OAc) ₂ Catalyst

Experiment number Ionic liquid % Conversion One Trihexyl (tetradecyl) phosphonium chloride 82 2 Trihexyl (tetradecyl) phosphonium triflate 92 3 Trihexyl (tetradecyl) phosphonium tripleamide 62 4 Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate 100 5 Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate 100 6 Trihexyl (tetradecyl) phosphonium diisobutyl phosphinate 100 7 Trihexyl (tetradecyl) phosphonium decanoate 100 8 Trihexyl (tetradecyl) phosphonium tetrafluoroborate 60 9 Trihexyl (tetradecyl) phosphonium hexafluorophosphate 82

Table 8

Hex-Coupling Reaction of Iodobenzene and Ethylacrylate in Various Ionic Liquids Using Pd (OAc) ₂ Catalyst

Experiment number Ionic liquid % Conversion One Trihexyl (tetradecyl) phosphonium chloride 42 2 Trihexyl (tetradecyl) phosphonium triflate 78 3 Trihexyl (tetradecyl) phosphonium tripleamide 52 4 Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate 84 5 Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate 10 6 Trihexyl (tetradecyl) phosphonium diisobutyl phosphinate 86 7 Trihexyl (tetradecyl) phosphonium decanoate 87 8 Trihexyl (tetradecyl) phosphonium tetrafluoroborate 35 9 Trihexyl (tetradecyl) phosphonium hexafluorophosphate 76

Example 8: Pd (OAc) ₂ Carbonylation of Iodobenzene in Various Ionic Liquids Using Catalysts

The general reaction procedure is as follows:

To the stirred and jacketed reactor was added 1.0 g of iodobenzene, 3 equivalents of triethylamine, 6 equivalents of ethanol, catalytic amount of Pd (OAc) ₂ and 2.0 g of phosphonium ion liquid. The reaction mixture was heated at 120 ° C. for 14 hours under a CO partial pressure of 5 bar. After 14 hours, the reaction mixture was cooled to room temperature and the total reaction mixture was poured into water. The reaction mixture was extracted with petroleum ether (3x30 ml) and the total organic phase was washed with water and then concentrated in vacuo and then distilled under reduced pressure. The ethylbenzoate product was recovered in almost quantitative yield.

The phosphonium ionic liquid solvent in this experiment was selected from the following groups:

Trihexyl (tetradecyl) phosphonium chloride;

Trihexyl (tetradecyl) phosphonium triflate;

Trihexyl (tetradecyl) phosphonium tripleamide;

Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate;

Trihexyl (tetradecyl) phosphonium decanoate; And

Butylmethylimidazolium [bmin] hexafluorophosphate.

As shown in Table 9, all ionic liquids yielded the required product in near quantitative yield while completely consuming the starting iodobenzene. In the case of trihexyl (tetradecyl) phosphonium decanoate, a mixed product was obtained in which 50% of the product was a decanoate ester and 50% of the expected ethyl ester, with the decanoate anion acting as a nucleophile, resulting in an intermediate It clearly shows attacking Ar-Pd-CO-X species.

This experiment clearly confirms the particular suitability of the phosphonium phosphinate compounds of the present invention for palladium catalyzed carbonylation of aryl halides.

Table 9

Carbonylation of Iodobenzene in Various Ionic Liquids with Pd (OAc) ₂ Catalyst

Experiment number Ionic liquid yield% One Trihexyl (tetradecyl) phosphonium chloride 100 2 Trihexyl (tetradecyl) phosphonium triflate 97 3 Trihexyl (tetradecyl) phosphonium tripleamide 100 4 Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate 100 5 Trihexyl (tetradecyl) phosphonium decanoate 50 + 50 6 [bmin] hexafluorophosphate 78

Example 9: Pd (OAc) ₂ Synthesis of Bipyridine Through Homocoupling of Bromopyridine in Various Ionic Liquids Using Catalyst

The following components were added to the stirred and jacketed reactor:

Bromopyridine 1.0g

Isopropanol 2.0g

K ₂ CO ₃ 1.5g

Pd (OAc) ₂ 0.03 g

The reaction mixture was heated at 120 ° C. for 36 hours in a phosphonium ion liquid solvent selected from the following group:

Trihexyl (tetradecyl) phosphonium triflate;

Trihexyl (tetradecyl) phosphonium tripleamide;

Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate;

Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate;

Trihexyl (tetradecyl) phosphonium decanoate.

The total yields of bipyridine synthesized using different solvents were evaluated and presented in Table 10. The yield of bipyridine was significantly different depending on the solvent selected. Excellent yields were obtained when the phosphonium phosphinate compounds of the invention were used as solvents, which resulted in bipyridine synthesis via homocoupling of bromopyridine in various ionic liquids using Pd (OAc) ₂ catalyst. The suitability of the compound could be confirmed.

Table 10

Synthesis of bipyridine by homocoupling bromopyridine using Pd (OAc) ₂ catalyst in various phosphonium ion liquids

Experiment number Ionic liquid yield% One Trihexyl (tetradecyl) phosphonium dicyclohexyl phosphinate 52 2 Trihexyl (tetradecyl) phosphonium decanoate 100 3 Trihexyl (tetradecyl) phosphonium bis- (2,4,4'-trimethylpentyl) phosphinate 52 4 Trihexyl (tetradecyl) phosphonium tripleamide 43 5 Trihexyl (tetradecyl) phosphonium triflate 36

Claims (20)

A compound of formula (I) Formula I In this expression, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom or a hydrocarbyl group, provided that at most two of R ₁ to R ₄ and at most one of R ₅ and R ₆ are hydrogen ; Y ₁ is O or S; Y ₂ is O or S. The compound of claim 1, wherein each of R ₁ , R ₂ , R ₃ , R ₄ , R _5, and R ₆ is independently an alkyl group of 1 to 30 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, or 2 to 30 carbon atoms. To alkenyl groups, 2 to 30 alkynyl groups, 6 to 18 carbon atoms, or an aralkyl group. _{3. A} compound according to claim 2, wherein each of R ₁ , R ₂ , R ₃ and R ₄ is independently an alkyl group of 5 to 20 carbon atoms. 4. A compound according to claim 3, wherein each R ₁ , R ₂ and R ₃ is n-hexyl and R ₄ is n-tetradecyl. The compound according to any one of claims 1 to 4, wherein each R ₅ and R ₆ is independently an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms, an alkynyl of 2 to 30 carbon atoms A compound characterized by being a group, an aryl group having 6 to 18 carbon atoms or an aralkyl group. _{6. A} compound according to claim 5, wherein each R ₅ and R ₆ is independently an alkyl group of 5 to 20 carbon atoms. A compound according to claim 1, wherein R ₅ and R ₆ are 2,4,4'-trimethylpentyl and Y ₁ and Y ₂ are O. 2. A compound according to claim 1, wherein R ₅ and R ₆ are isobutyl and Y ₁ and Y ₂ are O. The method of claim 1 wherein R ₅ and R ₆ are cyclohexyl and Y ₁ and Y ₂ are O. The method of claim 1 wherein R ₅ and R ₆ are isobutyl and Y ₁ and Y ₂ are S. The compound according to claim ₁ , wherein the total carbon number in R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is 25 or more. The compound according to any one of claims 1 to 11, wherein the total carbon number in R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is 40 or more. The compound according to any one of claims 1 to 12, which is incompatible with water. 10. A compound according to any one of claims 1 to 9, wherein Y ₁ and Y ₂ are both O. The compound of any one of claims 1-6 and 10, wherein Y ₁ and Y ₂ are both S. 12. i) a process for preparing a phosphonium phosphinate compound of formula (I) as described in claim 1 characterized by reacting a compound of formula (II) with ii) a compound of formula (IV) Formula II Formula IV Wherein R ₁ to R ₄ are as described in claim 1, X ^- is the leaving group, R ₅ , R ₆ , Y ₁ and Y ₂ are as described in claim 1, M ^{k +} is H ⁺ or a metal cation having a valence of "k". The method of claim 16, wherein M ^{k +} is H ⁺ and X ⁻ is OH ⁻ . The method of claim 16, wherein M ^{k +} is H ⁺ , X ⁻ is a leaving group other than OH ⁻ , and the reaction is carried out in the presence of a base. The process of claim 16 wherein M ^{k +} is a metal cation having a valence of “k” and X ⁻ is a leaving group other than OH ⁻ . Use as a solvent of the compound of any one of Claims 1-15.