PROCESS FOR THE PRODUCTION OF 17-Oxabicyclo[14.1.0]heptadec-8-ene

Abstract

The invention relates to a process for producing 17-oxabicyclo[14.1.0]heptadec-8-ene comprising a reaction with the reactants cyclohexadeca-1,9-diene and hydrogen peroxide.

Claims

1. Process for producing 17-oxabicyclo[14.1.0]heptadec-8-ene comprising a reaction with the reactants, cyclohexadeca-1,9-diene and hydrogen peroxide.

2. Process according to claim 1, characterized in that the reaction is carried out in a two-phase system.

3. Process according to claim 1 or 2, characterized in that the reaction is carried out in the presence of a catalyst.

4. Process according to one of the foregoing claims, characterized in that the catalyst contains phosphorus.

5. Process according to one of the foregoing claims, characterized in that the catalyst contains tungsten.

6. Process according to one of the foregoing claims, characterized in that the active species of the catalyst contains a peroxotungstophosphate.

7. Process according to one of the foregoing claims, characterized in that the active species of the catalyst contains the anion, {PO.sub.4[WO(O.sub.2).sub.2].sub.4}.sup.3.

8. Process according to one of the foregoing claims, characterized in that the active species of the catalyst contains a cation of a phase transfer catalystpreferably, a tetraalkylammonium cation.

9. Process according to one of the foregoing claims, characterized in that the active species of the catalyst contains a cation of a phase transfer catalyst of the formula,
R.sup.1.sub.nR.sup.2.sub.mN.sup.+, characterized in that R.sup.1 and R.sup.2 each mean C1-C30 n-alkyl, and R.sup.1 is the same as or different from R.sup.2, and the sum of m and n is 4.

10. Process according to one of the foregoing claims, characterized in that the active species of the catalyst is formed from at least one phosphorus-containing acid, at least one tungsten (VI)-compound, and at least one phase transfer catalystpreferably, in situ.

11. Process according to claim 10, characterized in that the phosphorus-containing acid is selected from phosphoric acid, phosphonic acids, phosphinic acids, and heteropoly acids and their derivatives, the tungsten (VI)-compound is selected from alkali tungstates, alkaline-earth tungstates, ammonium tungstates, or tungsten trioxide monohydratepreferably, sodium tungstateor/and the phase transfer catalyst is selected from a tetraalkylammonium saltpreferably, a compound of the formula,
(R.sup.1.sub.nR.sup.2.sub.mN.sup.+).sub.yX.sup.y, characterized in that R.sup.1 and R.sup.2 each mean C1-C30 n-alkyl, and R.sup.1 is the same as or different from R.sup.2, X.sup.y-equals Cl.sup., Br.sup., I.sup., HSO.sub.4.sup., SO.sub.4.sup.2, H.sub.2PO.sub.4.sup., HPO.sub.4.sup.2, PO.sub.4.sup.3, CH.sub.3SO.sub.3.sup., CF.sub.3SO.sub.3.sup., CH.sub.3C.sub.6H.sub.4SO.sub.3.sup., ClO.sub.3.sup., ClO.sub.4.sup., or NO.sub.3.sup., and the sum of m and n equals 4, and y equals 1, 2, or 3.

12. Aqueous mixture for use as a catalyst precursor in a process according to one of the foregoing claims, comprising at least one phosphorus-containing acid, at least one tungsten (VI)-compound, and at least one phase transfer catalyst.

13. Compound of the formula,
[R.sup.1.sub.nR.sup.2.sub.mN.sup.+].sub.3{PO.sub.4[WO(O.sub.2).sub.2].sub.4}, characterized in that R.sup.1 and R.sup.2 each mean C1-C30 n-alkyl, and R.sup.1 is the same as or different from R.sup.2, and the sum of m and n is 4, for use as active species of a catalyst in a process according to one of the foregoing claims.

Description

DESCRIPTION OF THE INVENTION

[0004] The process for producing 17-oxabicyclo[14.1.0]heptadec-8-ene comprises a reaction in which cyclohexadeca-1,9-diene and hydrogen peroxide are used as reactants.

[0005] The molecular relationship of cyclohexadeca-1,9-diene to hydrogen peroxide is, preferably, 1 less than 1, more preferably, 1:0.1-0.9, and, particularly preferably, 1:0.4-0.6.

[0006] Cyclohexadeca-1,9-diene and its production are already known, and it is also available commercially. It is often present as a mixture of stereoisomers.

##STR00001##

[0007] Hydrogen peroxide (H.sub.2O.sub.2) and its production are likewise already known, and it is also available commercially.

[0008] A further advantage of the process is that there exists no compelling need to use halogen-containing solvents in the reaction, so that the reaction can be carried out without halogenated solventsin particular, solvents containing chlorine. In this respect, the need to dispose of the halogenated solvent is eliminated, and there is no danger that undesired halogenated organic compounds will form. Halogen-free solvents such as aliphatic or cyclic hydrocarbons and alkylated aromatics are preferred.

[0009] The reaction of cyclohexadeca-1,9-diene and hydrogen peroxide can be carried out in a two-phase system. For example, this can be accomplished by adding to the reactants either no solvent or only very nonpolar solvents (such as toluene) or very polar solvents (such as water).

[0010] It is advantageous to use a catalyst in the process, wherein phosphorus-containing or/and tungsten-containing catalysts are especially suitable. Furthermore, the use of a phase transfer catalyst is also advantageous.

[0011] The catalyst and its active species are preferably allowed to develop in situ as catalyst precursors. One of the advantages of in situ formation consists in the fact that, unlike ex situ formation, the active species need not be isolated in order to be able to be used in the process. Phosphorus-containing catalyst precursors include, e.g., phosphoric acid, phosphonic acids such as hydroxymethylphosphonic acid and aminomethylphosphonic acid, phosphinic acids such as diphenylphosphinic acid or di(hydroxymethyl)phosphinic acid, and heteropoly acids such as tungstophosphoric acid or molybdophosphoric acid and their derivatives (e.g., lacunar heteropoly acids and polyoxometalates). A variation in the precursor of the phosphorus component is also possible. Therefore, in addition to H.sub.3PO.sub.4, phosphonic acids are very well suited. Hydroxymethylphosphonic acid and phenylphosphonic acid are particularly preferred in this instance.

[0012] Tungsten-containing catalyst precursors include, for example, water-soluble tungsten compounds, tungstates, tungsten(VI)-compounds, alkali tungstates, alkaline-earth metal tungstate, ammonium tungstate, or tungsten trioxide monohydrate. Na.sub.2WO.sub.4 is a specific example of a tungsten-containing catalyst precursor.

[0013] Examples of a phase transfer catalyst include tetraalkylammonium salt(s) or, preferably, one or more compounds of the formula,

(R.sup.1.sub.nR.sup.2.sub.mN.sup.+).sub.yX.sup.y,

characterized in that [0014] R.sup.1 and R.sup.2 each mean C1-C30 n-alkyl, and R.sup.1 is the same as or different from R.sup.2, and the sum of m and n is 4,
X.sup.y equals Cl.sup., Br.sup., I.sup., HSO.sub.4.sup., SO.sub.4.sup.2, H.sub.2PO.sub.4.sup., HPO.sub.4.sup.2, PO.sub.4.sup.3, CH.sub.3SO.sub.3.sup., CF.sub.3SO.sub.3.sup., CH.sub.3C.sub.6H.sub.4SO.sub.3.sup., ClO.sub.3.sup., ClO.sub.4.sup., or NO.sub.3.sup., and the sum of m and n equals 4, and y equals 1, 2, or 3.

[0015] Preferred anions of the phase transfer catalyst include hydrogen sulfate anions, sulfonic acid anions, or dihydrogen phosphate anions, with hydrogen sulfate anions being particularly preferred.

[0016] One example of a phase transfer catalyst is Aliquat 336 (trioctylmethylammonium chloride).

[0017] It is advantageous if 1 to 3 methyl groups are located on the ammoniacal nitrogen, wherein the remaining alkyl groups on the ammoniacal nitrogen should then have a greater chain length of between 6 and 30 carbon atoms in the chain, with a preferred chain length being between 8 and 22 carbon atoms.

[0018] When mixing the tungsten and phosphate-containing catalyst precursors in the presence of hydrogen peroxide and water, peroxotungstophosphates are generated. It is assumed that many suitable peroxotungstophosphates have the {PO.sub.4[WO(O.sub.2).sub.2].sub.4}.sup.3 anion available.

[0019] The cationic component of the active species of the catalyst can be formed from the cation of a phase transfer catalyst; in particular, the cation of the phase transfer catalyst can have the formula,

R.sup.1.sub.nR.sup.2.sub.mN.sup.+, [0020] characterized in that R.sup.1 and R.sup.2 each mean C1-C30 n-alkyl, and R.sup.1 is the same as or different from R.sup.2, [0021] and the sum of m and n is 4.

[0022] To produce the active species of the catalyst, an aqueous mixture/solution comprising at least one phosphorus-containing acid, at least one tungsten (VI) compound, and at least one phase transfer catalyst and, as the case may be, hydrogen peroxide, can be used. Table A contains examples of the tungsten-containing and phosphorus-containing catalyst precursors and phase transfer catalysts of such aqueous solutions.

TABLE-US-00001 TABLE A Tungsten- Phosphorus- containing containing catalyst catalyst Ex. No. precursor precursor Phase transfer catalyst 1 Na.sub.2WO.sub.4 HOCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]Cl 2 Na.sub.2WO.sub.4 HOCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 3* Na.sub.2WO.sub.4 HOCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.18H.sub.37).sub.3N]HSO.sub.4 4 Na.sub.2WO.sub.4 C.sub.6H.sub.5P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]Cl 5 Na.sub.2WO.sub.4 C.sub.6H.sub.5P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 6* Na.sub.2WO.sub.4 C.sub.6H.sub.5P(O)(OH).sub.2 [CH.sub.3(C.sub.18H.sub.37).sub.3N]HSO.sub.4 7 Na.sub.2WO.sub.4 H.sub.2NCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]Cl 8 Na.sub.2WO.sub.4 H.sub.2NCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 9 Na.sub.2WO.sub.4 H.sub.3PO.sub.4 [(C.sub.4H.sub.9).sub.4N]HSO.sub.4 10 Na.sub.2WO.sub.4 H.sub.3PO.sub.4 [CH.sub.3(C.sub.8H.sub.17).sub.3N]Cl 11 Na.sub.2WO.sub.4 H.sub.3PO.sub.4 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 12* Na.sub.2WO.sub.4 H.sub.3PO.sub.4 [(CH.sub.3).sub.2(C.sub.18H.sub.37).sub.2N]HSO.sub.4 13* Na.sub.2WO.sub.4 H.sub.3PO.sub.4 [(C.sub.18H.sub.37).sub.4N]HSO.sub.4 14 Na.sub.2WO.sub.4 H.sub.3PO.sub.4 [(CH.sub.3).sub.3(C.sub.16H.sub.33)N]O.sub.3SC.sub.6H.sub.4- 4-CH.sub.3 15* Na.sub.2WO.sub.4 H.sub.3PO.sub.4 [CH.sub.3(C.sub.8H.sub.17).sub.3N]H.sub.2PO.sub.4 16 Na.sub.2WO.sub.4 (C.sub.6H.sub.5).sub.2P(O)OH [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 17 Na.sub.2WO.sub.4 H.sub.2NCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 18 Na.sub.2WO.sub.4 H.sub.3PO.sub.4 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 19 Na.sub.2WO.sub.4 HOCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 20 Na.sub.2WO.sub.4 (HOCH.sub.2).sub.2P(O)OH [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 21 Na.sub.2WO.sub.4 (HOCH.sub.2).sub.2P(O)OH [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4

[0023] The invention also comprises one or more compounds of the formula,

[R.sup.1.sub.nR.sup.2.sub.mN+].sub.3{PO.sub.4[WO(O.sub.2).sub.2].sub.4}, [0024] characterized in that [0025] R.sup.1 and R.sup.2 each mean C1-C30 n-alkyl, and R.sup.1 is the same as or different from R.sup.2, and the sum of m and n is 4.

[0026] These compounds can be used as active species of a catalyst in the inventive process and are generated by the mixing of the already named catalyst precursors and phase transfer catalysts in water in the presence of hydrogen peroxide. Examples of these compounds include

[CH.sub.3(C.sub.8H.sub.17).sub.3N].sub.3{PO.sub.4[WO(O.sub.2).sub.2].sub.4},

[(CH.sub.3).sub.2(C.sub.8H.sub.17).sub.2N].sub.3{PO.sub.4[WO(O.sub.2).sub.2].sub.4},

[CH.sub.3(C.sub.18H.sub.37).sub.3N].sub.3{PO.sub.4[WO(O.sub.2).sub.2].sub.4},

[(C.sub.4H.sub.9).sub.4N].sub.3{PO.sub.4[WO(O.sub.2).sub.2].sub.4},

[(CH.sub.3).sub.2(C.sub.18H.sub.37).sub.2N].sub.3{PO.sub.4[WO(O.sub.2).sub.2].sub.4},

[(C.sub.18H.sub.37).sub.4N].sub.3{PO.sub.4[WO(O.sub.2).sub.2].sub.4}, and

[(CH.sub.3).sub.3(C.sub.16H.sub.33)N].sub.3{PO.sub.4[WO(O.sub.2).sub.2].sub.4}.

[0027] The inventive process may also comprise a separation step, such as a separation of the phases, distillation, or/and a chromatographic separation.

[0028] The process may be conducted discontinuously or continuously.

[0029] The following examples clarify the invention, without limiting it in any way.

General Protocol for Examples 1-15 (Table 1)

[0030] Na.sub.2WO.sub.4 (0.165 g, 0.50 mmol), H.sub.3PO.sub.4, or one of the listed phosphonic acids (0.50 mmol) and a phase transfer catalyst (0.50 mmol) were placed in a 50 mL three-necked flask. 1,9-Cyclohexadecadiene (mixture of isomers, 25 mmol, 5.51 g), H.sub.2O (5.00 g) and toluene (20.00 g) were subsequently added. Two phases were formed: an organic phase consisting of toluene and CHDD, and an aqueous phase containing the precursors for the catalyst. The mixture was then stirred at 800 rpm and heated to the reaction temperature of 60 C. Once this temperature was reached, the first portion of H.sub.2O.sub.2 (50 wt %) (0.47 g, 6.91 mmol, 0.27 mol. equiv.) was added and the reaction started. After 60 min, a second portion of H.sub.2O.sub.2 was dripped in (0.47 g, 6.91 mmol, 0.27 mol. equiv.). Thereafter, it was stirred for another 2 hours at 60 C. The progress of the reaction was monitored by taking samples from the organic phase every 20 minutes during the first two hours and at the end of the experiment. The determination of conversion, yields, and selectivities was carried out by means of GC/MS.

TABLE-US-00002 TABLE 1 Phosphorus Conversion Yield Selectivity Examples component Phase transfer catalyst t [min] of CHDD [%] of I [%] to I [%] 1 HOCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]Cl 80 11.4 11.4 100 100 16.3 15.9 97.3 180 30.1 27.7 92.1 2 HOCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 20 11.8 11.8 100 40 22.1 21.1 95.6 60 22.7 21.7 95.2 80 29.2 27.2 93.2 3* HOCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.18H.sub.37).sub.3N]HSO.sub.4 20 12.5 12.5 100 40 21.6 20.1 93.3 60 24.2 22.4 92.5 4 C.sub.6H.sub.5P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]Cl 100 14.8 14.8 100 120 19.2 18.3 95.7 180 25.7 23.8 92.7 5 C.sub.6H.sub.5P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 60 19.3 18.5 95.6 80 25.2 23.8 94.5 100 31.6 29.0 91.7 6* C.sub.6H.sub.5P(O)(OH).sub.2 [CH.sub.3(C.sub.18H.sub.37).sub.3N]HSO.sub.4 60 19.4 18.3 94.3 80 24.3 22.7 93.7 100 31.3 28.8 92.1 7 H.sub.2NCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]Cl 60 14.8 14.5 97.9 80 23.3 22.4 96.2 100 32.5 30.2 93.0 8 H.sub.2NCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 60 13.2 13.1 99.2 80 23.8 22.5 94.6 100 34.5 31.7 91.8 9 H.sub.3PO.sub.4 [(C.sub.4H.sub.9).sub.4N]HSO.sub.4 120 0 0 0 10 H.sub.3PO.sub.4 [CH.sub.3(C.sub.8H.sub.17).sub.3N]Cl 20 15.8 13.2 83.6 60 29.4 25.1 85.4 100 42.1 34.4 81.8 11 H.sub.3PO.sub.4 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 20 10.9 10.7 98.7 40 23.8 22.7 95.3 60 28.7 26.6 92.7 12* H.sub.3PO.sub.4 [(CH.sub.3).sub.2(C.sub.18H.sub.37).sub.2N]HSO.sub.4 20 10.1 10.1 100 40 20.7 19.4 93.7 80 37.8 34.5 91.4 13* H.sub.3PO.sub.4 [(C.sub.18H.sub.37).sub.4N]HSO.sub.4 60 6.7 6.5 97.2 80 14.4 14.0 97.4 100 23.9 22.6 94.5 120 31.1 28.4 91.2 14 H.sub.3PO.sub.4 [(CH.sub.3).sub.3(C.sub.16H.sub.33)N]O.sub.3SC.sub.6H.sub.4-4-CH.sub.3 60 12.0 12.0 100 120 24.1 23.0 95.4 180 33.7 31.1 92.1 15* H.sub.3PO.sub.4 [CH.sub.3(C.sub.8H.sub.17).sub.3N]H.sub.2PO.sub.4 40 18.6 18.1 97.1 60 23.5 22.4 95.3 80 31.1 28.5 91.5 100 37.1 33.8 90.9 *A one-half approach was taken with Example 15 (Table 1), using the following amounts: Na.sub.2WO.sub.4 (0.083 g, 0.25 mmol), H.sub.3PO.sub.4 (0.25 mmol), PTC (0.25 mmol), 1,9-cyclohexadecadiene (2.75 g, 12.5 mmol), toluene (10.0 g), and H.sub.2O (2.5 g), and 2 portions of 50 wt % H.sub.2O.sub.2 (0.24 g, 3.53 mmol, each 0.28 mol. equiv.). The reaction procedure was carried out exactly as described in the general protocol for Examples 1-14.

Protocol for Example 16 (Table 2)

[0031] Na.sub.2WO.sub.4 (0.083 g, 0.25 mmol), diphenylphosphinic acid (0.054 g, 0.25 mmol), and methyltrioctylammonium hydrogen sulfate (0.25 mmol) were placed in a 25 mL, three-necked flask. 1,9-Cyclohexadecadiene (mixture of isomers, 12.5 mmol, 2.75 g), H.sub.2O (2.50 g), and toluene (10.00 g) were subsequently added. Two phases were formed: an organic phase consisting of toluene and CHDD, and an aqueous phase containing the precursors for the catalyst. The mixture was then stirred at 800 rpm and heated to the reaction temperature of 80 C. Once this temperature was reached, the first portion of H.sub.2O.sub.2 (50 wt %) (0.24 g, 3.53 mmol, 0.28 mol. equiv.) was added and the reaction started. After 60 min, a second portion of H.sub.2O.sub.2 was dripped in (0.24 g, 3.53 mmol, 0.28 mol. equiv.). Thereafter, it was stirred for another 2 hours at 80 C. The progress of the reaction was monitored by taking samples from the organic phase every 20 minutes during the first two hours and at the end of the experiment. The determination of conversion, yields, and selectivities was carried out by means of GC/MS.

TABLE-US-00003 TABLE 2 Phosphorus Phase transfer Conversion Yield Selectivity Example component catalyst t [min] of CHDD [%] of I [%] to I [%] 16 (C.sub.6H.sub.5).sub.2P(O)OH [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 20 0.2 0.2 99.0 40 2.0 2.0 99.0 60 3.2 3.1 99.0 80 6.2 6.1 99.0 100 11.7 11.3 96.6 120 16.2 15.6 95.9 180 24.1 22.4 93.0 240 28.6 26.0 90.9

Protocol for Example 17 (Table 3)

[0032] Na.sub.2WO.sub.4 (0.165 g, 0.50 mmol), aminomethylphosphonic acid (0.50 mmol) and methyltrioctylammonium hydrogen sulfate (0.233 g, 0.50 mmol) were placed in a 50 mL three-necked flask. 1,9-Cyclohexadecadiene (mixture of isomers, 25 mmol, 5.51 g), H.sub.2O (5.00 mL), and 1,2-dichloroethane (20.00 mL) were subsequently added. Two phases were formed: an organic phase consisting of 1,2-dichloroethane and CHDD, and an aqueous phase containing the precursors for the catalyst. The mixture was then stirred at 700 rpm and heated to the reaction temperature of 60 C. Once this temperature was reached, the first portion of H.sub.2O.sub.2 (50 wt %) (1.10 g, 16.2 mmol, 0.65 mol. equiv.) was added and the reaction started. After 30 min and 60 min, a second portion of H.sub.2O.sub.2 was dripped in (1.10 g, 16.2 mmol, 0.65 mol. equiv. per portion) in each case. Thereafter, it was stirred for another 1.5 hours at 60 C. The progress of the reaction was monitored by taking samples from the organic phase every 20 minutes during the first 100 minutes and at the end of the experiment. The determination of conversion, yields, and selectivities was carried out by means of GC/MS.

TABLE-US-00004 TABLE 3 Phosphorus Phase transfer Conversion Yield Selectivity Example component catalyst t [min] of CHDD [%] of I [%] to I [%] 17 H.sub.2NCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 20 5.3 5.3 99.0 40 12.4 12.4 99.0 60 25.1 23.5 93.5 80 36.6 33.4 91.3 100 44.9 40.0 89.0

Protocol for Example 18 (Table 4)

[0033] H.sub.2WO.sub.4 (0.125 g, 0.50 mmol), phosphoric acid (0.50 mmol) and methyltrioctylammonium hydrogen sulfate (0.233 g, 0.50 mmol) were placed in a 50 mL three-necked flask. 1,9-Cyclohexadecadiene (mixture of isomers, 25 mmol, 5.51 g), H.sub.2O (5.00 mL), and toluene (20.00 mL) were subsequently added. Two phases were formed: an organic phase consisting of toluene and CHDD, and an aqueous phase containing the precursors for the catalyst. The mixture was then stirred at 700 rpm and heated to the reaction temperature of 60 CC. Once this temperature was reached, the first portion of H.sub.2O.sub.2 (50 wt %) (0.74 g, 10.9 mmol, 0.43 mol. equiv.) was added and the reaction started. After 30 min and 60 min, a second portion of H.sub.2O.sub.2 was dripped in (0.74 g, 10.9 mmol, 0.43 mol. equiv. per portion) in each case. Thereafter, it was stirred for another 1.5 hours at 60 CC. The progress of the reaction was monitored by taking samples from the organic phase every 20 minutes during the first 100 minutes and at the end of the experiment. The determination of conversion, yields, and selectivities was carried out by means of GC/MS.

TABLE-US-00005 TABLE 4 Phosphorus Phase transfer Conversion Yield Selectivity Example component catalyst t [min] of CHDD [%] of I [%] to I [%] 18 H.sub.3PO.sub.4 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 20 24.7 24.7 99.0 40 44.0 41.6 94.5 60 57.2 50.6 88.4

Protocol for Example 19 (Table 5)

[0034] Na.sub.2WO.sub.4 (0.165 g, 0.50 mmol), hydroxymethylphosphonic acid (0.50 mmol), and methyltrioctylammonium hydrogen sulfate (0.50 mmol) were placed in a 25 mL, three-necked flask. 1,9-cyclohexadecadiene (mixture of isomers, 25 mmol, 5.51 g) and H.sub.2O (5.00 g) were subsequently added. Two phases were formed: an organic phase consisting of CHDD and an aqueous phase containing the precursors for the catalyst. The mixture was then stirred at 800 rpm and heated to the reaction temperature of 60 C. Once this temperature was reached, the first portion of H.sub.2O.sub.2 (50 wt %) (0.47 g, 6.91 mmol, 0.27 mol. equiv.) was added and the reaction started. After 60 min, a second portion of H.sub.2O.sub.2 was dripped in (0.47 g, 6.91 mmol, 0.27 mol. equiv.). Thereafter, it was stirred for another 2 hours at 60 C. The progress of the reaction was monitored by taking samples from the organic phase every 20 minutes during the first two hours and at the end of the experiment. The determination of conversion, yields, and selectivities was carried out by means of GC/MS.

TABLE-US-00006 TABLE 5 Phosphorus Phase transfer Conversion Yield Selectivity Example component catalyst t [min] of CHDD [%] of I [%] to I [%] 19 HOCH.sub.2P(O)(OH).sub.2 [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 40 13.6 13.6 99.0 100 28.5 27.0 94.9 120 36.5 32.6 89.4

Protocol for Example 20 (Table 6)

[0035] Na.sub.2WO.sub.4 (0.083 g, 0.25 mmol), bis(hydroxymethyl)phosphinic acid (0.031 g, 0.25 mmol), and methyltrioctylammonium hydrogen sulfate (0.25 mmol) were placed in a 25 mL, three-necked flask. 1,9-Cyclohexadecadiene (mixture of isomers, 12.5 mmol, 2.75 g), H.sub.2O (2.50 g), and toluene (10.00 g) were subsequently added. Two phases were formed: an organic phase consisting of toluene and CHDD, and an aqueous phase containing the precursors for the catalyst. The mixture was then stirred at 800 rpm and heated to the reaction temperature of 60 C. Once this temperature was reached, the first portion of H.sub.2O.sub.2 (50 wt %) (0.24 g, 3.53 mmol, 0.28 mol. equiv.) was added and the reaction started. After 60 min, a second portion of H.sub.2O.sub.2 was dripped in (0.24 g, 3.53 mmol, 0.28 mol. equiv.). Thereafter, it was stirred for another 2 hours at 60 C. The progress of the reaction was monitored by taking samples from the organic phase every 20 minutes during the first two hours and at the end of the experiment. The determination of conversion, yields, and selectivities was carried out by means of GC/MS.

TABLE-US-00007 TABLE 6 Phosphorus Phase transfer Conversion Yield Selectivity Example component catalyst t [min] of CHDD [%] of I [%] to I [%] 20 (CH.sub.2OH).sub.2P(O)OH [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 20 2.5 2.5 99 40 6.3 6.3 99 60 11.3 11.3 99 80 20.8 20.5 98.6 100 29.2 28.4 97.3 120 32.4 30.7 94.9 180 45.7 40.8 89.3

Protocol for Example 21 (Table 7)

[0036] Na.sub.2WO.sub.4 (0.083 g, 0.25 mmol), bis(hydroxymethyl)phosphinic acid (0.031 g, 0.25 mmol), and methyltrioctylammonium hydrogen sulfate (0.25 mmol) were placed in a 25 mL, three-necked flask. 1,9-Cyclohexadecadiene (mixture of isomers, 12.5 mmol, 2.75 g), H.sub.2O (2.50 g), and toluene (10.00 g) were subsequently added. Two phases were formed: an organic phase consisting of toluene and CHDD, and an aqueous phase containing the precursors for the catalyst. The mixture was then stirred at 800 rpm and heated to the reaction temperature of 80 C. Once this temperature was reached, the first portion of H.sub.2O.sub.2 (50 wt %) (0.24 g, 3.53 mmol, 0.28 mol. equiv.) was added and the reaction started. After 60 min, a second portion of H.sub.2O.sub.2 was dripped in (0.24 g, 3.53 mmol, 0.28 mol. equiv.). Thereafter, it was stirred for another 2 hours at 80 C. The progress of the reaction was monitored by taking samples from the organic phase every 20 minutes during the first two hours and at the end of the experiment. The determination of conversion, yields, and selectivities was carried out by means of GC/MS.

TABLE-US-00008 TABLE 7 Phosphorus Phase transfer Conversion Yield Selectivity Example component catalyst t [min] of CHDD [%] of I [%] to I [%] 21 (CH.sub.2OH).sub.2P(O)OH [CH.sub.3(C.sub.8H.sub.17).sub.3N]HSO.sub.4 20 12.2 12.1 99.0 60 27.1 26.4 97.2 80 39.7 35.2 88.5 100 45.5 39.4 86.5 120 47.4 38.9 82.1