TWI298070B - Novel phosphonium phosphinate compounds and their methods of preparation - Google Patents

Description

1298070 A7 , · B7 V. INSTRUCTIONS (1) Scope of the invention: The present invention relates to novel phosphorous sulfate salts, a process for their preparation and their use, for example as a polar solvent. BACKGROUND OF THE INVENTION: The availability of low melting point or liquid cerium salts as polar solvents has been found to be referred to as π ionic liquids. The ionic liquid system provides an attractive alternative to traditional organic solvents used in chemical reactions. There are many reasons for this. For industrial purposes, the low vapor pressure system of ionic liquids is a very important feature. It is basically non-volatile, which is a kind of exclusion problem that is often encountered in eliminating traditional organic solvents. Because ionic liquids are often composed of poorly coordinating ions, they have the potential to provide highly polar and poorly coordinating solvents. Furthermore, many of these solvents are not miscible with conventional organic solvents, thus providing two A non-aqueous polar substitute for the phase system. Due to its unique solvent characteristics, it can be used to bring unusual combinations of reagents into the same phase. A recent review of the nature and use of ionic liquids is available in Thomas Welton's paper. The title is Μ room temperature ionic liquid, solvent for synthesis and catalysis" (Chem. Rev. 1999, 99, 2071-2083). The ionic liquid system provides a solvent with a wide liquid range and high thermal stability. However, there is still a need to increase the solvent selectivity available to chemists by developing novel ionic liquids with unique physical and chemical properties. SUMMARY OF THE INVENTION The present invention provides novel hypophosphorous acid scale compounds, and methods of preparing such compounds. The phosphoric acid scale compound can have a wide range of scale cations and a wide range of hypophosphite and dithiophosphinate anions. -4 - This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 B7 V. Description of invention (2) This novel hypophosphorous acid scale has the general formula (I)

Ri \ / r2 + Rs 丫1 / \ / P / \ P / R4 - \ R3 Ra' 丫 2 Formula (I) wherein: Each of Ri, R2, R3, R4, R5 and R6 is independently a hydrogen atom or a hydrocarbon group. , the condition is no more than two from R! to R4, and no more than one of R5 and R6 is hydrogen; Yi is 〇 or S; and Y2 is 〇 or S. Preferably, each to R6 is a hydrocarbon group. In another aspect, the invention provides a process for the preparation of a squara compound of formula (I) as defined above, wherein: i) is a compound of formula (II):

Ri R2 \ / X - (II)

P R4// R3 where 1^ to 114 are as defined above and C is a detachment basis. This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 B7 V. Description of invention ( 3 ii) Compound of formula (IV):

Wherein R5, R6, Yj and Y2 are as defined in formula (I), and Mk+ is Η+ or a metal cation having a valence bond "k". Preferably, if Mk+ is H+ and Wherein C is a leaving group other than OHT, the reaction is carried out in the presence of a base. If C is 〇tT and Mk+ is H+, no base is required. If Mk+ is a metal cation having a valence bond "k" X- is a cleavage group other than 〇Η·. Thus, in a specific embodiment, the compound according to formula (I) can be prepared by reacting the following: i) a compound of formula (II)

X - Formula (II) wherein R! to R4 are as defined above for formula (I), and x_ is a leaving group, such as hydroxide (〇 )), acetate, sulfate or halogen China National Standard (CNS) A4 Specification (210X 297 mm) 1298070 A7 B7 V. Description of Invention (4), preferably gas root, bromide or strontium root, and ii) compound of formula (III): H +

Wherein R 5 , R 6 , 丫丨 and Y 2 are as defined above for formula (I), and when } C of formula (II) is any de-bonding group other than ΟΗ·, iii) is used, for example A metal or soil hydroxide or carbonate of the soil. In another embodiment, the compound according to formula (I) can also be prepared by reacting a compound of formula (II) as defined above with ii) a compound of formula (IV):

Mk+

Wherein R5, R6, Yi and Y2 are as defined above for formula (I), and Mk+ is ammonium or metal, and k is the valence bond of the metal. Suitable metals are any metal which forms a water-soluble salt with an anion, such as a metal, preferably Na or 1C. -7 - This paper scale applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 1298070 A7 _ · B7 __ V. Description of the invention (5) In another aspect of the invention, the compound according to formula (I) Used as an ionic solvent. BRIEF DESCRIPTION OF THE DRAWINGS: The nature of the invention has been generally described, and a preferred embodiment will now be described with reference to the accompanying drawings in which: Figure 1 shows a bis(2,4, decyltrimethyl-pentyl)phosphoric acid trihexyl (fourteen bases) scale TGA test results. Figure 2 shows the results of TGA detection for trihexyl(tetradecyl)phosphonium diisobutylphosphinate. Figure 3 is a 31 P NMR spectrum of a trihexyl (tetradecyl) scale of dicyclohexylphosphite. Figure 4 shows the results of thermogravimetric analysis (TGA) for the trihexyl (tetradecyl) scale of dicyclohexylphosphite.

Figure 5 is a 31 P NMR spectrum of trihexyl-(tetradecyl) diisobutyl dithiophosphate. Figure 6 shows the results of TGA detection for trihexyl (tetradecyl) scale diisobutyl dithiophosphoric acid. DESCRIPTION OF THE PREFERRED EMBODIMENTS: The present invention relates to a compound of the formula (I) as defined above, wherein: each core, R2, R3, R4, R5 and Re are independently hydrogen or a hydrocarbyl group; Y! is 0 or S And Y2 is Ο or S. The group heart to Rg may bear a substituent or contain a hetero atom, provided that the substituent or hetero atom does not interfere with the preparation of the compound of the present invention and does not adversely affect the desired properties of the compound. Acceptable substituents include alkoxy, pitthio, ethanethio and # to a group, and acceptable heteroatoms include oxygen and sulfur. Substituents may increase the cost of the compounds of the invention, and 8 - this paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7

Therefore, it is important to cost. 'It is intended to cover the use of these compounds as a solvent. Therefore, in most cases, the base will not exist. Preferably, each ^^^ and & is an independent carbon atom (alkyl group, cycloalkyl group of 3 to 7 carbon atoms, 2 to 3 carbon atoms (fluorenyl group, 2 to 30 carbons) An alkynyl group of an atom, an aryl group of 6 to 18 carbon atoms, or an aryl fluorenyl group. A burning group of more than 18 carbon atoms, especially more than a carbon atom, may increase the cost. Since cost is an important factor in the manufacture of a solvent Therefore, it is intended to cover the fact that the alkyl group is typically not more than 2 gorgon atoms. Therefore, it is more preferably a compound according to formula (I), wherein each core, R3, && R6 is independently an alkyl group of 5 to 2 carbon atoms. For example, 'heart, R2, R3, R4, R5 and heart can be n-butyl, isobutyl, n-pentyl, 哀 戊Base, isopentyl, n-hexyl, cyclohexyl, (2,4,4L trimethyl)pentyl, % octyl, tetradecyl, etc., preferably preferably & at least one of the heart contains a relatively south carbon atom Number, for example 14 or more. In many cases, it is generally desirable that the heart to be & is not the same. For many purposes, it is generally desirable to have at least one of the heart to && contains a significantly higher number of carbon atoms. Among them, compounds with different R4 are called asymmetry. For many applications, it is preferred that both Υι and γ2 are 〇. For example, in the use of certain In the chemical reaction of a metal catalyst such as pd(〇Ac)2, it is preferred that both 'Υι and 丫2 are 〇, because the thio group is present in the sulfonate anion, which interferes with the action of the catalyst. Phosphoric acid rust compound, which is used as a solvent for chemical reaction not involving a metal catalyst. <Applicable to Chinese national standard fa; # 1298070 A7 B7 V. Description of invention (7) Preferred compounds include compounds according to formula (I) , wherein each of Ri, R 2 ' R 3 , & Rs and R 0 is independently aryl or substituted aryl. For example, one or more of Ri, heart, Han 3, anti 4, Rs and R0 may be It is a phenyl group, a phenethyl group, a tolyl group or a trial base. For some purposes, T, according to the formula (I), the compound is hydrophobic or, water is not mixed, 'is preferred.', water Insoluble, the term is intended to describe a two-phase system when mixed with water. a compound, but does not exclude an ionic liquid which will dissolve in water, and does not exclude an ionic liquid which will dissolve water, provided that a two-phase system is formed. Therefore, it has a large total number of carbons, equal to or greater than 20, and in particular greater than 25 or 26, or a compound having at least one aryl group, is preferred because it is more hydrophobic. Water immiscibility is a desirable feature of the hypophosphorous acid scale t, not only because it renders the compound useful for aqueous phase • Two-phase reaction, and when prepared according to certain methods, because it contributes to the purification and isolation of the sulphonic acid scale. For the total number of carbon atoms that can be present in & to & . However, this total cannot exceed 5 miles. For many purposes, substances that are liquid at room temperature are extremely valuable. Thus, preferred compounds are those in which the particular group heart to heart system is selected to produce a liquid that is liquid at room temperature. The degree to which a particular meaning is chosen to achieve a particular melting point and water incompatibility is within the skill of the artist, but may require some routine experimentation. For example, the asymmetry and branching of the core-to-heart of the cation or hypophosphite anion is an important determinant of the melting point. When the asymmetry and the degree of branching I are increased, the melting point tends to decrease. Branching can occur on alpha or Q carbon, or at any intermediate point. Increase the total number of carbon atoms present in the heart of the hydrocarbon base to the heart

1298070 A7

:Resistance:::Increase:::Sub:: The effect will be slightly asymmetry and branching properties ":: a sulfhydryl group as a compound of (4) and not a compound of two two two eleven groups and one heptyl group Different, not & both (four) sub-families have a total of 40 carbon atoms. For the purpose of the two purposes, 'the compound with the formula (1), may: =, because it enters a tender chemical reaction For the palm environment, an example has been given to a compound of the palm of the horse, which has a pair of palm atoms. According to formula (I) Examples of preferred compounds include those in which: each Ri, & and & is a n-hexyl group, and the heart is a positive tetradecyl group, and & and R0 is 2,4,4'-trimethylpentene a, and a and 1 are 〇; or the heart and heart are isobutyl, and 'and heart is 〇; or & & & is cyclohexyl, and 丫丨 and meaning are; or R5 and R6 are isobutyl The base, and Υι and Y2 are S. The present invention also provides a method for preparing a phosphoric acid scale compound according to Formula 1. In general, the scale of hypophosphorous acid can be obtained by formulating (π) scale salt with either: Phosphoric acid and alkali, 2) Prepared by reacting a hypophosphorous acid of the formula (IV). Alternatively, the sulphuric acid sulphate may be prepared by reacting a scale of the formula (II) with hypophosphorous acid. The reaction temperature is not critical, but the reaction may be conveniently carried out. Achieved at high temperatures, up to about 1 〇〇C' is preferably in the range of 45-70 C. The use of higher temperatures contributes to phase separation. If bismuth subphosphate is not miscible with water, it can be as follows To prepare, first mix the salt of formula (II) with the compound of formula (III) and water and stir or mix it, then add the base. Stir the mixture for a while. When -11 - this paper scale applies to China National Standard (CNS) A4 Specification (210 X 297 mm)

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Line 1298070 . A7 ______ B7 V. INSTRUCTION DESCRIPTION (9) When k is mixed, the reaction mixture will be separated into a product containing a hypophosphorous acid scale < an organic phase, and an aqueous phase. This aqueous phase can be decanted and the organic phase can then be washed with water to remove salt by-products formed by the reaction (e.g., sodium carbonate). If so, then residual water can be removed from the organic layer by, for example, hollow stripping. In a variation of the above method, the scale salt is first mixed with water. Then sodium hydroxide is added, and finally added. Tannic acid. When the mixing is stopped, the reaction mixture will separate into an aqueous phase and an organic phase which can be further processed as described in the above method. The dilute acid scale according to formula (I) which is immiscible with water can also be produced by mixing the scale salt of formula (II) with the hypophosphite of formula (IV) and water and stirring. The mixture is mixed with the W compound for a period of time, for example, one hour. When the mixing is stopped, the reaction mixture will separate into an aqueous layer and an organic layer. The aqueous layer can be decanted and the organic layer can be washed several times with water to remove any residual [M+][x-]k. If desired, the dissolved water can be removed from the organic layer by, for example, hollow stripping. Another preferred method can be used to prepare scales of phosphoric acid which are either miscible or immiscible with water. According to formula (I), the phosphoric acid scale can be obtained by reacting the formula (π) with a scale of water, which means that the compound of formula (π), wherein χ- is 〇Η·, reacts with the formula (ΠΙ) hypophosphorous acid to produce phosphoric acid scales and Made of water. The water produced by the acid-base reaction can be removed by, for example, hollow stripping. Since the acid which is produced by this method does not have to be washed with water to remove the salt, the method can be used to prepare phosphite which is miscible or immiscible with water. This method is preferably used to prepare hypophosphorus rust having a small total carbon number and a spectrum of 7 to 10 carbons. It should be noted that the compound of formula (I) contains up to six hydrocarbyl cores to %. Formula (1) - 12 - This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 B7 V. Description of invention (1〇) The specific properties of the compound are based on the six groups. Depending on the meaning, the choice of different meanings for such groups allows for precise tailoring of the properties of the compounds of the invention. Therefore, these compounds can be designed to be liquid at a specific temperature and water-immiscible. A change in the nature of one or more of the group's heart to R6 can be achieved. The presence of these six groups is advantageous for this purpose when compared to ionic liquids known to be based on dialkyl sulfonium cations, which have only two changes The group. The compound of the present invention has a density of less than 1. Therefore, it is composed of the upper phase in the two-phase system of water. In this respect, it differs from the ionic liquid known to be based on dimercapto cations, which tend to have a density of more than 1 and thus constitute a lower phase in the two phase systems of water. The decanoic acid salt of the invention can be used as a polar solvent. In a preferred embodiment, the phosphonium hypophosphite of the present invention can be used as a polar solvent for chemical reactions, such as Michael addition, aryl coupling, Diels-Alder, alkylation, two-phase catalysis, Heck reaction, Hydrogenation, or for enzyme reactions, such as lipase reactions. In the following examples (see Examples 5 and 6), it will be confirmed that the hypophosphorous acid squama of the present invention is a suitable solvent for the synthesis of biphenyl via high coupling of bromobenzene or iodobenzene. Biaryl groups are of great importance in synthetic organic chemistry because they have found many industrial and pharmaceutical applications. For example, the endurance of liquid crystals often relies on the synthesis of a biaryl structure. It is particularly important to produce the biaryl molecular substructure in the stagnation of the product biotin and steganacin in the day of the eve. Therefore, it is produced in a cost effective manner. Ullman -13- of the biaryl type This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 , . B7 V. Invention Description (11) Synthesis, typically requires high temperature conditions (200°) C), and need to wait for the amount of copper. The use of an I bar catalyst with a suitable ionic solvent, such as the sour acid acid scale of the present invention, avoids the need for stoichiometric metals and high temperatures. In Example 8, the suitability of the phosphorous acid scale as a solvent for palladium-catalyzed carbonylation was confirmed. The palladium-catalyzed carbonylation of aryl-X derivatives is a powerful and powerful method for the synthesis of various aromatic carboxylic acid derivatives, such as guanamines and esters. The aryl-rich species formed as an intermediate is subjected to easy CO insertion, followed by nucleophilic attack of alcohol, water and amines, and the respective acids, esters and guanamines are obtained. This reaction can be carried out using an aryl halide with carbon monoxide and a nucleophile in the presence of a catalytic amount of a compound. Other metal catalysts derived from Co and Ni have also been used as catalysts. As can be seen from the following examples, some of which are according to the invention, some of which are comparative examples, The choice of solvent in the reaction changes. In many instances, the hypophosphorous acid squama of the present invention achieves good or good results. Therefore, it is a synergistic effect in the synthesis method. Example: Example 1: Bis(2,4,4'-trimethyl-pentyl)phosphoric acid trihexyl (tetra-tetrayl) scaly (2,4,4'-trimethyl-pentyl) The trihexyl (tetradecyl) rust was prepared according to the following method. Filled in a 5 liter stirred jacketed reactor: 1.880 moles of trihexyl (tetradecyl) scale (1003 grams of CYPHOS 3653, containing 97.2. Trihexyl chloride (tetradecyl) scales) -14- The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " --------- Factory·> ·5_. '7 ^ r?

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1298070 A7 _' '___^B7___ V. Description of invention (12) 1.875 Moss (2,4,4'-trimethylpentyl) hypophosphorous acid (625 g CYANEX 272, containing 87% bis (2,4, 4f-trimethylpentyl)phosphoric acid) and 1369 grams of water. After heating the mixture to 54 ° C, 25 ° / was added over about 32 minutes. Aqueous sodium hydroxide solution (82.3 g, 97% sodium hydroxide (two moles), 236.8 g water). The two phases were stirred at 55 ° C for an additional 1/2 hour. The agitation is then turned off and the reaction mixture is separated into a two phase system comprising an upper organic phase and a lower aqueous phase (phase separation takes about 2 minutes). The lower aqueous phase was decanted, and the upper organic layer was washed with about 1300 g of distilled water each time, washed three times by stirring, and passed at 55 ° C for one hour. The amount of time required for the overall phase separation is increased with each successive wash for 2 minutes, 30 minutes, and then for the final wash, which takes 8 minutes to achieve an overall separation, but for the organic layer to clarify, it takes 22 hours. . After washing and allowing the liquid phase to separate, the organic layer is then stripped to remove the dissolved water. After stripping to 125 ° C under a pressure of 4 mm Hg, approximately 230 grams of water (13.2% by weight) was removed. Finally the organic layer is completely transparent. Results The gas ions of the aqueous phase were analyzed (see Table 1). The first decantation removed 82·9. /. Chloride. The first, second and third washes were additionally removed by 12% and 1.7. . And 0.2. /. Gas ions, a total of 96.70 / 〇. Analysis of the bis(2,4,4f-trimethylpentyl)phosphoric acid trihexyl (tetradecyl) scale by TGA was found to have a thermal stability of about 300 C (see Figure 1). This analysis also showed that the product could contain up to 4-60 Torr of water. -15- This paper scale applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 1298070 A7 ' ' B7 V. Description of invention (13 ) Table 1 Double (2,4,4'-trimethylpentyl) Preparation of trihexyl (tetradecyl) scale diphosphate (2,4,[trimethyl 87.0% R,2P(0)0H Rn=bis 2,4,[trimethylpentyl)phosphoric acid pentyl (CYANEX 272) CYPHOS 3653 97.2% R3 RTC1 R = n-butyl 2.1% R3 PCI R > = n-tetradecyl 0.2% HC1 chloride balance. z. Cl Weight (g) Moer % Cl Molar C1 was removed CYANEX 272 625 1.875 0.000 CYPHOS 3653 1003 1.880 1.946 97% NaOH 82.3 1.996 0.000 Water 1605 1st decantation 1404 4.0720 1.613 82.9 2nd decantation 1283 0.6450 0.233 12.0 3rd decantation 1305 0.0873 0.032 1.7 4th decantation 1303 0.0096 0.004 0.2 Total 1.882 96.7 Example 2: Trihexyl ditetradecylphosphoric acid (tetradecyl) rust diisobutylphosphinate trihexyl (fourteen The base is made according to the following method. Filled in a 5 liter stirred jacketed reactor: 2·0〇4 mol of trihexyl chloride (tetradecyl) scale (1069 g CYPHOS 3653) 2.004 mol diisobutyl hypophosphorous acid (390.8 g, 91· 3 〇〇 diisobutyl decanoic acid) and 1114 g water - 16 - This paper scale applies to Chinese National Standard (CNS) Α 4 specification (210 X 297 mm) 1298070 A7 B7

After the mixture was heated to 55 ° C, 25 was added over 30 minutes. ,. Aqueous sodium hydroxide solution (87.7 g, 97. cesium hydroxide (two moles), 24 gram of water). The two phases were stirred at 55 ° C for an additional hour. The agitation was then turned off and the reaction mixture was separated into a two phase system comprising the upper organic phase and the lower aqueous phase (phase separation took about 2 minutes). The lower aqueous phase was decanted, and the upper organic layer was washed three times by stirring at 55 ° C for one hour, using about 1,300 g of distilled water each time. The amount of time required for the overall phase separation increases with each successive wash. After washing, the organic and liquid phases were initially cloudy but clarified upon standing overnight. After washing and allowing the liquid phase to completely separate, the organic layer is then stripped to remove dissolved water. The strip was stripped to 丨^乇^ under a pressure of 4 mm Hg to remove approximately 13.4 by weight. water. Finally the organic layer is completely transparent. Results The chloride ions of the aqueous phase were analyzed (see Table 2). The first decantation removed 63.7% of the gas ions. The first, second and third washes were additionally removed 5·3〇. , oh, 3. . And 〇·2. . Chloride ion, a total of 69.5%. A sample of trihexyl (tetradecyl) diisobutylphosphinate was analyzed by TGA and it was found that the thermal stability reached about 30 (TC (see Figure 2). This analysis also showed that the product ^ contained up to 4-6 〇/〇. Table 2 Preparation of dihexylbutylphosphoric acid trihexyl (tetradecyl) scale Diisobutylphosphinophosphoric acid 91.3% R,, 2 P(〇)〇H Isobutyl CYPHOS 3653 97.2% R3 RTCl 2.1% R3 PCI 0.2% HC1 R==n-butyl-n-tetradecyl-17- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 ' ' B7 V. Invention description (15 Chloride balance % C1 Weight (g) Moer °〇C1 Mo C1 is removed R"2 Ρ(0)0Η 390.8 2.004 0.000 CYPHOS 3653 1069 2.004 2.074 97 °〇NaOH 87.7 2.127 0.000 Water 1354 1st pour Analysis 1245 3.7610 1.321 63.7 2nd decantation 1278 0.3051 0.110 5.3 3rd decantation 1270 0.0174 0.006 0.3 4th decantation 1300 0.0090 0.003 0.2 Total 1.440 69.5 Example 3: Trihexyl dicyclohexylphosphite (tetradecyl) The hexacyclohexylphosphoric acid trihexyl (tetradecyl) squama is prepared according to the following method. Stirring in a jacketed reactor: 1.907 mol of trihexylphosphonium chloride (tetradecyl) hydrazine (1017 g CYPHOS 3653) 1.909 dicyclohexyl phosphate (349 g of dicyclohexyl phosphate) 2.417 mol And 1200 grams of water, after heating the mixture to 55 ° C, add 25 ° / within 30 minutes. An aqueous solution of sodium hydroxide (83.4 g of sodium hydroxide (2.022 mol), 210 g of water). The two phases were stirred at 55 ° C for an additional hour. The agitation was then turned off and the reaction mixture was separated into a two phase system comprising the upper organic phase and the lower aqueous phase (phase separation took about 4 minutes). The lower aqueous phase was decanted, and the upper organic layer was washed three times by stirring with 1300 g of distilled water. -18- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 B7 V. Description of invention (16) After washing and allowing liquid phase separation, the organic layer is then stripped and stripped to Remove dissolved water. After stripping to 138 ° C under a pressure of 4 mm Hg, approximately 210 g of water (14 wt Q / water) was removed. Finally the organic layer is completely transparent. Results The chloride ions of the aqueous phase were analyzed. The first decantation removed 82.2. . Chloride ions, while the first, second and third washes additionally removed 14.7%, 1_70/〇 and 0.2% chloride, for a total of 98.80/〇 (see Table 3). A sample of the organic layer was analyzed by 31 P NMR (Fig. 3). NMR spectroscopy showed two unique signals: +33.46 ppm for squamous cations and +31.2741 ppm for sub-pure anion, consistent with the reaction product dicyclohexylphosphoric acid trihexyl (tetradecyl) scale 0 by TGA analysis of dicyclohexyl A sample of trihexyl phosphate (tetradecyl) scale was found to have a thermal stability of approximately 300 ° C (see Figure 4). This analysis also shows that the product can contain up to 7-8% moisture. Table 3 Preparation of dicyclohexylphosphoric acid trihexyl (tetradecyl) scale Dicyclohexylphosphinic acid 98.0% Rn2 Ρ(0)0Η Rn=cyclohexyl CYPHOS 3653 97.2% R3 RTCl R=n-butyl 2.1% R3 PCI Positive-tetradecyl 0.2% HC1 chloride balance. 〇 Cl Weight (g) Mohr α. Cl Moer Cl is removed R,, 2 Ρ(0)0Η 439 1.909 0.000 CYPHOS 3653 1017 1.907 1.973 97 °〇NaOH 83.4 2.022 0.000 Water 1200 -19- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 B7 V. Description of invention (17) 1st decantation 1249 4.6040 1.622 82.2 2nd decantation 1344 0.7650 0.290 14.7 3rd decantation 1300 0.0898 0.033 1.7 4th decantation 1310 0.0090 0.003 0.2 Total 1.948 98.8 Table 4 Water from the sub-phosphoric acid scale R^P RMP(Q)0 stripped R" Water removed. /〇 Temperature (°C) Pressure (mm Hg) 2,4,4'-three Methylpentyl 13.2 125 4 isobutyl 13.4 135 4 cyclohexyl 14.0 138 4 Example 4: Trihexyl (tetradecyl) bis-isobutylphosphoryl dithiophosphoryl dihexyl diisopropylate The scales were prepared according to the following procedure: Filled in a stirred jacketed reactor: 1.91 moles of trihexyl (tetradecyl) scale (1019 grams of CYPHOS 3653) 1.99 molar diisobutyl disulfide Sodium hypophosphite (925 g AEROPHINE 3418A, 50% diisobutyl dithiophosphoric acid in water) and 1500 g water mixed The mixture was heated to 50 ° C and stirred for 30 minutes. The stirring was then turned off and the reaction mixture was separated into a two-phase system comprising the upper organic phase and the lower aqueous phase (phase separation took about 4 minutes). The lower aqueous phase was decanted. And the upper organic layer was washed three times by stirring with 1400 g of distilled water at 50 ° C. Next, the organic layer was stripped to 125 ° C under a pressure of 1.2 mm Hg. Only ___-20-_ paper The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 B7 V. Description of invention (18) Remove 25 grams of water. Finally the organic layer is completely transparent. Result _ The final product is liquid at room temperature The vapor content is 0.0099%. The 3 1 P NMR spectrum shows two unique signals: +33.37 ppm squamous cations; and +65.81 ppm dithiomethalin anions (Figure 5). Analysis of diisobutyl disulfide by TGA A sample of trihexylphosphoric acid (tetradecyl) scale was found to have a thermal stability of approximately 270 ° C (see Figure 6). This analysis also showed that the product contained approximately 0.5 ° water. Example 5: In various scale ionic liquids, Use Pd (OAc\, high mate interaction via bromobenzene Biphenyl into this series of experiments, high conjugation of bromobenzene, in various scales based ionic liquid. The reaction is carried out according to the following:

In the following experiment, the stirred jacketed reactor was charged: 1.0 g of bromobenzene, 2.0 g of isopropanol, 1.5 g of K2C〇3, 0.03 g of Pd(〇Ac)2, and the reagents were dissolved in a scaly ionic liquid solvent. Heating at 120 ° C for 16 hours -- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 B7 V. Inventive Note (19), the solvent is selected from including Trihexyl (tetradecyl) scale of dicyclohexylphosphinic acid; trihexyl (tetradecyl) sulphate; bis-(2,4,4,-trimethylpentyl)phosphoric acid trihexyl (tetradecyl) Scale; trifluoromethanesulfonamide trihexyl (tetradecyl) scale; and trihexyltrifluoromethanesulfonate (tetradecyl) scale. The reaction mixture was cooled, poured into 50 mL of water and the mixture was extracted with petroleum ether (at 45-60 ° C). This ionic liquid forms an intermediate layer which can be recovered. The petroleum ether layer was washed with water, then brine, and concentrated. The residue is distilled to obtain the desired biaryl compound. The total yield of biphenyl using different solvents was evaluated and is listed in Table 5. The yield of biphenyl varies considerably with the choice of solvent. However, both experiments, in which a quasi-phosphoric acid scale compound was used as a solvent, gave a substantially higher yield than a comparative experiment in which trifluoromethane was used to burn the amine scale or trifluoromethane acid scale as a solvent. Thus, the suitability of the compounds of the present invention for use in the synthesis of Pd(〇Ac)2i biphenyl was demonstrated for high coupling via bromobenzene. The reaction conditions are not optimized for any particular solvent, and it is reasonable to expect that the overall yield can be improved. Table 5 Biphenyl synthesis in various scale ionic liquids using Pd(OAc)2 via high coupling of bromobenzene. Experimental No. Ionic liquid Yield. 7. 1 Dicyclohexylphosphinic acid trihexyl (tetradecyl) scale 61 2 decanoic acid trihexyl (tetradecyl) scale 1 〇〇 ___-22- _ This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 'B7 V. Description of the invention (2〇) 3 bis-(2,4,4-trimethylpentyl)phosphoric acid trihexyl (tetradecyl) scale 52 4 trifluoromethanesulfonamide Trihexyl (tetradecyl) scale 26 5 trihexyltrifluoromethanesulfonate (tetradecyl)phosphonium 9 Example 6: Pd (0Act as a catalyst) in various ionic liquids via high-coupling of iodobenzene Biphenyl Synthesis The following reaction was similar to the reaction of Example 5 except that it was carried out using iodobenzene as a starting material. Filling in a stirred jacketed reactor: 1.0 g of benzene breaking 1.5 g of isopropanol 1.5 g ^: 03 0.03 g Pd(〇Ac)2 These reagents were heated in a hydrazine ionic liquid solvent at 120 ° C for 18 hours. The solvent was selected from the group consisting of: trihexyl (tetradecyl) ruthenium; trifluoromethane Trihexyl (tetradecyl) sulfonate; trifluoromethanesulfonamide trihexyl (tetradecyl) scale; bis-(2,4,4'-trimethylpentyl)hypophosphorous acid Hexyl (tetradecyl) scale; dicyclohexylphosphoric acid trihexyl (tetradecyl) scale; diisobutylphosphoric acid trihexyl (tetradecyl) scale; trihexyl citrate (tetradecyl) scale; tetrafluoro Trihexyl (tetradecyl) sulfonate; and trihexyl (tetradecyl) hexafluoroate. The total yield of biphenyl using different solvents was evaluated and listed in Table 6. ___-23-___ The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 B7 V. INSTRUCTIONS (21) The yield of biphenyl varies considerably with the choice of solvent. Use gasified trihexyl ( The tetrabasic scale as a solvent causes a particularly low biphenyl yield because chloride ions interfere with the Pd(〇Ac)2 catalyst. When the phosphoric acid scale compound according to the present invention is used as a solvent, the reaction system is highly productive. The rate is carried out at a spectrum of about 100. These results confirm that the bismuth subphosphite compound does not interfere with the Pd(〇Ac)2 catalyst, and therefore uses Pd(〇Ac)2 as a touch through the high coupling of iodine. Suitable solvents for the synthesis of biphenyls in the medium. Table 6 Pd (OAc) in various ionic liquids 2 Catalyst iodobenzene high coupling cooperation experiment number ionic liquid conversion rate. / 1 gasification trihexyl (tetradecyl) scale 13 2 trifluoromethanesulfonic acid trihexyl (tetradecyl) scale 100 3 Fluoromethanesulfonamide trihexyl (tetradecyl) rust 72 4 bis-(2,4,4-trimethylpentyl)phosphoric acid trihexyl (tetradecyl) scale 78 5 dicyclohexylphosphoric acid trihexyl ( Fourteen base) scale 100 6 diisobutylphosphoric acid trihexyl (tetradecyl) scale 100 7 decanoic acid trihexyl (tetradecyl) scale 100 8 tetrafluoroborate tetrakis (tetradecyl) scale 56 9 hexafluoride Trihexyl sulphate (tetradecyl) scale 50 Example 7: Heck coupling of iodobenzene with methyl acrylate using PcKOAct catalyst in various ionic liquids

V<H H COOCH

Pd(0Ac)2, K2C〇3 scale ionic liquid

H/==C\〇OH -24 - This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 ' B7 V. Invention description (22) in a stirred jacketed reactor Packing: 1.0 g of iodobenzene 0.86 g of methyl acrylate 2.0 £K2C 〇 3 0. 05 g of Pd(OAc) 2 The reaction mixture was heated in a solution of 2.0 g of hydrazine ionic liquid at 80 ° C for 14 hours. Selected from the group consisting of: trihexyl (tetradecyl) chloride; trihexyltrifluoromethanesulfonate (tetradecyl) scale; trifluoromethanesulfonamide trihexyl (tetradecyl) scale; double-(2,4 , 4f-trimethylpentyl)phosphoric acid trihexyl (tetradecyl) scale; dicyclohexylphosphoric acid trihexyl (tetradecyl) scale; diisobutylphosphoric acid trihexyl (tetradecyl) scale; Trihexyl (tetradecyl) scale; trihexyl (tetradecyl) scale of tetrafluoroborate; and trihexyl (tetradecyl) hexafluoroantimonate. The total yield series is shown in Table 7. The yield of the reaction varies considerably with the choice of solvent. About 100°/. The yield of the spectrum was obtained using three kinds of phosphoric acid scale solvents of the present invention, thus confirming that the hypophosphorous acid scale compound provides a suitable solvent for the Heck coupling reaction. A similar series of experiments was carried out using ethyl acrylate instead of methyl acrylate. The results of these experiments are shown in Table 8. In general, the Heck coupling of iodobenzene with ethyl acetoacetate is less coupled than the coupling of toluene with acrylic acid methyl vinegar to obtain lower yields. However, from this experiment, the phosphoric acid scale of the present invention has been clarified _-25-_ This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1298070 A7 B7 V. Inventive Note (23) Compound, This is to provide a suitable solvent for this Heck coupling reaction. Table 7 Heck coupling of benzene and propionate methyl ester using Pd(OAc)2 catalyst in various ionic liquids. Experimental No. Ionic liquid conversion. 1 trihexyl chloride (tetradecyl) scale 82 2 trifluoromethanesulfonic acid trihexyl (tetradecyl) scale 92 3 trifluoromethanesulfonamide trihexyl (tetradecyl) scale 62 4 double - (2, 4,4-trimethylpentyl)phosphoric acid trihexyl (tetradecyl) scale 100 5 dicyclohexylphosphoric acid trihexyl (tetradecyl) scale 100 6 diisobutylphosphoric acid trihexyl (tetradecyl) Rust 100 7 Trihexyl citrate (tetradecyl) scale 100 8 Tetrafluoroborate tetrahexyl (tetradecyl) scale 60 9 hexafluoroantimonate trihexyl (tetradecyl) scale 8 82 In various ionic liquids, The Heck coupling experiment number of ionic liquid conversion using iodobenzene and propionate ethyl ester of Pd(OAc)2 catalyst. /. 1 Trihexyl chloride (tetradecyl) scale 42 2 Trifluoromethane (tetradecyl) scale of trifluoromethanesulfonate 78 3 Trifluoromethanesulfonamide trihexyl (tetradecyl) scale 52 4 double-(2,4 ,3-trimethylpentyl)phosphoric acid trihexyl (tetradecyl) scale 84 5 dicyclohexylphosphoric acid trihexyl (tetradecyl) scale 10 6 diisobutylphosphoric acid trihexyl (tetradecyl) scale 86 7 Trihexyl citrate (tetradecyl) scale -26- 87 This paper scale applies to Chinese National Standard (CNS) A4 specification (210 x 297 mm) 1298070 A7 B7 V. Description of invention (24) 8 Tetrafluoroborate III Hexyl (tetradecyl) scale 35 9 hexafluorodecanoic acid trihexyl (tetradecyl) scale 76 Example 8 · In various ionic liquids, the carbonylation of PeKOAc and the catalyst iodobenzene is generally carried out. Said to proceed:

HNu

Pd(〇Ac)2, triethylamine, 393K scale ionic liquid

R = H, complete Nu = nucleophile, such as OH, OR, NHR · Packed in a stirred jacketed reactor: 1.0 g of iodobenzene, 3 equivalents of triethylamine, 6 equivalents of ethanol, catalytic amount of Pd ( 〇Ac) 2 and 2.0 g of hydrazine ionic liquid. The reaction mixture was heated at 120 ° C for 14 hours under a partial pressure of 5 bar C0. After 14 hours, the reaction mixture was allowed to reach room temperature and the total reaction mixture was poured into water. The reaction mixture was extracted with petroleum ether (3.times.30 mL), and the organic phase was washed with water and concentrated in sputum and then distilled under reduced pressure. The ethyl benzoate product was recovered in almost quantitative yield. For the purposes of these experiments, the hydrazine ionic liquid solvent is selected from the group consisting of: gasified trihexyl (tetradecyl) scale; trihexyl trifluoromethanesulfonate (tetradecyl) scale; trifluoromethanesulfonamide trihexyl (tetradecyl) scale; bis-(2,4,4'-trimethylpentyl)phosphoric acid trihexyl (tetradecyl) scale; trihexyl citrate (tetradecyl) scale; and hexafluoro-diuretic acid Butylmethyl imipen [bmin]. As shown in Table 9, all ionic liquids are obtained in almost quantitative yields. -27- This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 1298070 A7 B7 V. Description of invention (25 The product material is required and the initial iodobenzene is completely consumed. In the case of a trihexyl (tetradecyl) decanoate, a mixture of products is obtained, wherein 50°'/. The product is a phthalate ester, and 50 ° /. It is the expected ethyl ester; apparently the citrate anion acts as a nucleophile and attacks the intermediate Ar-Pd-CO-X species. These experiments demonstrate the particular suitability of the phosphite scale compounds of the present invention for the palladium catalyzed carbonylation of aryl halides. Table 9 Carbonylation of iodobenzene using Pd(OAc)2 catalyst in various ionic liquids Experiment No. Ionic liquid yield % 1 Trihexyl chloride (tetradecyl) scale 100 2 trifluoromethanesulfonic acid Trihexyl (tetradecyl) scale 97 3 trifluoromethane decylamine trihexyl (tetradecyl) scale 100 4 bis-(2,4,4-trimethylpentyl)phosphoric acid trihexyl (tetradecyl) ) scale 100 5 trihexyl citrate (tetradecyl) scale 50 + 50 6 six-image phosphoric acid [bmin] 78 Example 9: in various ionic liquids, using PcKOAcY catalyst, through the high coupling of bromopyridine The pyridine synthesis was charged in a stirred jacketed reactor: 1.0 g of bromo-based p-precipitate 2.0 g of isopropanol 1.5 g 〖2 (:03 0.03 g of Pd(OAc)2 The reaction mixture was placed in a rust-ionic liquid solvent, Heating at 120 °C 36 ________-28-__ This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Binding

Line 1298070 A7 'B7 V. Description of the invention (26) hours, the solvent is selected from the group consisting of: trihexyl trifluoromethanesulfonate (tetradecyl) scale; trifluoromethanesulfonamide trihexyl (tetradecyl) scale; Bis-(2,4,4f-trimethylpentyl)phosphoric acid trihexyl (tetradecyl) front; dicyclohexylphosphoric acid trihexyl (tetradecyl) scale; and trihexyl decanoate (tetradecyl) scale. The total yield of bipyridine using different solvents was evaluated and is listed in Table 10. The yield of bipyridyl varies considerably with the choice of solvent. Good yields were obtained using the hypophosphorous acid scale compounds of the present invention as a solvent, and thus it was confirmed that these compounds were used in various ionic liquids using a Pd(OAc) 2 catalyst via a high coupling of bromopyridine. Suitability for pyridine synthesis. Table 10 In the various scale ionic liquids, using Pd(OAc)dization, bipyridyl synthesis by high coupling of bromopyridine, experimental number ionic liquid yield % 1 dicyclohexylphosphoric acid trihexyl (ten Tetrakis) scale 52 2 trihexyl decanoate (tetradecyl) scale 100 3 bis-(2,4,4-trimethylpentyl)phosphoric acid trihexyl (dec. 52 tetrayl) 铧 4 trifluoromethanesulfonate Amine trihexyl (tetradecyl) scale 43 5 trihexyl trifluoromethanesulfonate (tetradecyl) scale 36 __-29- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

1298070 f 69ii〇533 number patent application six "^ gas special core & whole ^ too ‘ 1. A compound of formula (I): Formula (I) wherein: each of R1, h, R3, R4, R5 and R6 is independently a hydrogen atom, provided that R1M4h exceeds two, ^, is hydrogen, · 5 6 + more than one Υ is 〇 or S; and Y2 It is 0 or S; the restriction condition is that the compound is tetra-n-butyl scale of diphenylphosphoric acid, tetra-n-butyl phenyl benzoate or tetraoctyl phenyl phosphate. 2. The compound according to claim 1, wherein each of the cores, κ, h, R4, R5 and R0 is independently an alkyl group of 1 to 30 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, 2 An alkenyl group to 30 carbon atoms, an alkynyl group of 2 to 30 carbon atoms, an aryl group of 6 to 18 carbon atoms, or an aralkyl group. 3. A compound according to claim 2, wherein each of Ri, &, heart and R4 is independently an alkyl group of 5 to 20 carbon atoms. 4. A compound according to claim 3, wherein each of the cores, r2 and & is n-hexyl' and R4 is a n-tetradecyl group. The compound according to any one of claims 1 to 4, wherein each R5 and the chemical system are independently an alkyl group of 1 to 30 carbon atoms, and 2 to 30 carbon atoms are 77176-960713.DOC-1 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm). 1298070 Patent application for the alkenyl group, an alkynyl group of 2 to 30 carbon atoms, or an aralkyl group. 6. A compound of 5 to 20 carbon atoms is formed according to the compound of the scope of claim patent. 7. The compound trimethylpentyl according to the scope of the patent application, and 丫1 and 丫2 are 〇. 8. The compound base according to item 1 of the patent application, and 1 and ¥2 are 〇. 9. The compound according to the scope of the patent application; base, and Y] and Y2 are 〇. 10. According to the patent application scope, the compound, base, and Υ2 are S. U. A compound according to claim 1 wherein the total number of carbons in &, r2, R3, R4, R5 and R6 is from 25 to 18 〇. 12. The compound according to claim 1, wherein the total number of slaves in Ri, r2, 3 R4 R5 and 6 is 40 to 180. β. A compound according to the scope of the patent application, which is insoluble with water. !4. According to the compound of item i of the scope of the patent, wherein & ::·根=Please refer to the compound of item i of the patent range, wherein γ2 is all. According to the formula 1 of the patent application, the first step is to make the compound of the formula (π): 6 to 18 carbon atoms, wherein each of the cores and the heart is unique, wherein R5 and R6 are 2, 4, 4, - R5 and R6 are isobutylene, wherein R5 and R6 are cyclohexyl and their centers are different from each other. 77176-960713.DOC _ 2 _ This paper scale is suitable for ai^^—(CNS) A4 specification _χ297 public love) 1298070 ABCD P r2 X is defined in the formula (II), and wherein & to the heart is as the de-base of the patent application range i τ, and ii) the compound of the formula (IV): Mk+ (IV) 丫 2 where W YlAY2 is defined in the patent and Mk + is H+ or a metal cation having a valence bond "k". Π. According to f, please special (four) around $ 〗 6 methods, its towel ... for mine, good for ΟΪΓ. 18. The method according to claim 6, wherein Mk + is a ore and X- is a leaving group other than OH, and the reaction is carried out in the presence of a base. The method of claim 16, wherein Mk + is a metal cation having a valence bond ' kn , and χ - is a leaving group other than 〇 h —. 20. A compound according to the scope of patent application No. 1 as a polar solvent 77176-960713.DOC Small This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) ABCD 1298070 VI. Patent application Use. 21. According to the compound of claim 1, wherein 1^112 is 3114? + is a trihexyl (tetradecyl) anthracene and a bis(2,4,4'-tridecylpentyl)phosphoric acid . 22. A compound according to claim 1 wherein LR2R3R4P+ is a trihexyl (tetradecyl) scale and RsR^YiYJ. is diisobutylphosphinate. 23. A compound according to claim 1 wherein 1^112 and 3114?+ are trihexyl (tetradecyl) scale roots and RsR^YiYzP. is a dicyclohexylidene hypophosphite. 24. The compound according to claim 1, wherein RiR2R3R4P + is a trihexyl (tetradecyl) scale root and RsR^YiYaP. is diisobutyl dithiophosphate. 77176-960713.DOC - 4 - This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)