Background of the Invention The halogenation of aldehydes and ketones is an important process. The known method for halogeration uses a large amount of AlCl3, which is a catalyst in these reactions. The amount of AlCl3 used sometimes reaches 2-3 mole AlCl3 to 1 mole-aldehydes or ketones. This leads to a large amount of wastes, which needs difficult and expensive treatment. A representative reaction, which will be referred to hereinafter for the purpose of illustration, is the bromination of 4-fluorobenzaldehyde (FBA).

4-Fluoro-3-phenoxybenzaldehyde (FPBA) is an intermediate for the production of pyrethroid insecticides. Preparation of 3-bromo-4- fluorobenzaldehyde (BFBA), which is used as an intermediate in the production of FPBA, is carried out, according to the known art, by the catalytic bromination of 4-fluorobenzaldehyde, using AlCl3 as the catalyst.

The preparation of FPBA from p-fluorobenzaldehyde (FBA) is disclosed in DE 2933979. The yield of the FBA in that process is only 57%, and a large amount of AlCl3 is used as a catalyst in the bromination. There are other methods for preparing FPBA with other reagents, for instance, p-toluidine, p-fluorotoluene and p-fluorobenzonitrile (J. Indian Chem. Soc. 21,112-116 (1944).; Rec. Trav. Chim. 82 (1963); DE 3008158).

It is a purpose of the invention to provide an improved process for the halogenation of aldehydes and ketones.

It is another purpose of the invention to provide a novel process for the preparation of 3-bromo-4-fluorobenzaldehyde, which overcomes the drawbacks of the prior art.

It is yet another purpose of the invention to provide a process for the preparation of 3-bromo-4-fluorobenzaldehyde, which does not require the use of large amounts of AlCl3 catalyst.

It is still another purpose of the invention to provide an efficient process for the preparation of 3-bromo-4-fluorobenzaldehyde, which does not require expensive purification processes, and the product of which can be used"as is"in the process for the preparation of 4-fluoro-3-phenoxybenzaldehyde.

Other objects and advantages of the invention will become apparent as the description proceeds.

Summary of the Invention The invention is directed to a process for the bromination and chlorination of aldehydes and ketones, comprising reacting the aldehyde or ketone with bromine or chlorine in oleum, optionally in the presence of iodine. The amount of iodine employed and vary from about 0-10%, and typically is in the range 0.5-5% by weight, relative to the substrate which is to be brominated (chlorination).

In another aspect, the invention is directed to a process for the preparation of 3-bromo-4-fluorobenzaldehyde and 3-chloro-4-fluorobentaldelyde (CFBA), which process comprises brominating 4-fluoro-benzaldehyde (FBA) or chlorinating FBA in oleum, optionally in the presence of iodine.

According to a preferred embodiment of the invention, the oleum contains <BR> <BR> <BR> <BR> about 1-65% free S03. Preferably, but non-limitatively, the oleum contains<BR> <BR> <BR> <BR> <BR> about 20-50% free S03.

While a broad range of iodine contents is permissible, according to a preferred embodiment of the invention, iodine is present in an amount of about 0-5 weight % relative to FBA, preferably but not limitatively 0.5-3 weight % relative to FBA.

As will be apparent to a person skilled in the art, the process of the invention can proceed in a very broad range of temperatures. According to a preferred embodiment of the invention, however, the reaction temperature is kept between about 0-100°C. According to a preferred embodiment of the invention the reaction temperature is between 30-60°C.

The oleum/FBA weight ratio can vary within a broad range. According to a preferred embodiment of the invention, however, the oleum/FBA weight ratio is between about 1.5 and 10.

The Br2/FBA molar ratio is also variable within a broad range, typically in the range 0. 4-1.0. According to a preferred embodiment of the invention the Br2/FBA molar ratio is in the range 0.50-0.65.

The C12/FBA nolar ratio is a variable within a broad range, typically in the range 0.5-1.0.

In another aspect, the invention is directed to a process for the preparation of 4-fluoro-3-phenoxy benzaldehyde, comprising the steps of : a) brominating 4-fluoro-benzaldehyde according to the process described above; b) acetalizing the crude 3-bromo-4-fluorobenzaldehyde obtained in step (a), without prior isolation thereof, to yield 3-bromo-4- fluorophenyldioxolane; c) condensing the 3-bromo-4-fluorophenyldioxolane of step (b) with potassium phenolate; d) hydrolyzing the 4-fluoro-3-phenoxyphenyldioxolane obtained in step (c), to yield 4-fluoro-3-phenoxybenzaldehyde.

A number of illustrative and non-limitative embodiments of the invention will now be described with reference to the examples to follow. The abbreviations used throughout this specification are as follows: BFBA-3-Bromo-4-fluorobenzaldehyde BFPD-3-Bromo-4-fluorophenyl dioxolane BPPD-3-Bromo-4-phenoxyphenyl dioxolane DBFBA-Dibromo-4-fluorobenzaldehyde DBFPD-Dibromo-4-fluorophenyl dioxolane DPPD-Bromo-4-phenoxyphenyl dioxolane EDC-Dichloroethane DCM-Dichloromethane FBA-4-Fluorobenzaldehyde FPD-4-Fluorophenyl Dioxolane FPPD-4-Fluoro-3-phenoxyphenyl dioxolane FPBA-4-Fluoro-3-phenoxybenzaldehyde GC-Gas chromatography GC/MS-Gas chromatography/Mass spectroscopy IFBA-3-Iodo-4-fluorobenzaldehyde IFPD-3-Iodo-4-fluorophenyl dioxolane PBFB-Pentabromofluorobenzene TBFBA-Tribromo-4-fluorobenzaldehyde BCBA-3-Bromo-4-chlorobenzaldehyde CBA-4-Chlorobenzaldehyde Example 1 Preparation of BFBA bv the bromination of FBA in oleum Into a half-liter flask equipped with a mechanical stirrer, a condenser, a thermometer and a dropping funnel, were introduced, at room temperature and with stirring, 100 g oleum (65% free S03) and 0.2 g iodine. 40 g (0.32 mole) FBA was added dropwise over one hour at a temperature in the range 30-40°C, then about 28 g bromine was added dropwise over 2 hours. The Br/FBA molar ratio was 0.55. Stirring was continued for an additional 2 hours at 30-400C. Samples were removed during the bromination to check the reaction conversion by GC analysis.

After completion of the reaction, 100 g. water was added carefully and then 120 g. dichloroethane. After separation of the lower organic layer, the aqueous acidic phase was extracted again with 100 g. water. After solvent stripping, 62 g. crude BCBA, with a purity of ca. 92% (GC, area), was obtained. The yield was about 88%.

The results of this specific example are detailed in Table II, Experiment No.

67.

Several similar experiments were carried out. The reaction conditions and the results of the experiments are set forth in Tables I, II and III below.

Table I Bromination of 4-fluorobenzaldehyde (FBA) in oleum (FBA-23.5 g. 0.19 mole, Br2/FBA mol. ratio-0.6) Exp. No. Iodine oleum oleum Temp. Time FBA BFBA IFBA DBFBA 1 % w/w conc./FBA DBFBA2 FBA % SOa w/w °C hr % GC % GC °/GC % GC 13680-6-20 10 35-45 5. 0 95. 0 3. 9-0/0.3 13680-8 3 20 7. 5 40 10. 0 4. 3 88. 4 1.2 0.7/2.2 13680-9 3 20 7. 5 60 6. 0 1. 5 86. 1 1.6 1.2/3.6 13680-2 5 20 10 30-44 5 3. 6 90. 5 1.4 0.7/2.0 13680-7* 5 20 7. 5 40-44 6. 5 2. 8 91. 5 1.4 0.7/2.5 13680-10* 5 20 7. 5 50 7. 0 0. 7 88. 6 2.0 1.1/3.9 13680-4 5 20 5 70-5 20. 3 72. 2 1.2 0.7/1.5 100 13680-3 5 98% 10 70-98 5 97. 1 1. 4 0.1 H2SO4 13680-12* 5 30 7. 5 30 6 1. 2 92. 3 2.1 0.8/2.2 13680-13* 5 25 7. 5 29 7 1. 1 92. 7 1.2 0.7/2.1 13680-14** 5257. 53081. 690. 82. 40. 8/2.2 *FBA-124 g, 1 mole **FBA-248 g, 2 mole ***PBFB was not included in Table I.

Table II<BR> Bromination of 4-fluorobenzaldehyde (FBA) in oleum<BR> (FBA - 12.4 g. 0.19 mole, Br2/FBA mol. ratio - 0.55; GC analysis of the reaction mixture @ Exp. Iodine oleum SO3/ Temp Time FBA BFBA IFBA DBFBA1 TBFBA PBFB No. w/w weight FBA °C hr %GC %GC %GC DBFBA2 %GC %GC FBA conc. g mol ratio %GC % SO3 36668- 3 200 10 2.0 30-40 4 27.6 59.5 1.7 0.6/1.5 0.2 2.0 89 14 6.0 79.1 1.7 0.8/2.0 1.4 2.6 36668- 3 300 5 1.5 30-40 4 72.1 25.9 - - - 1.0 90 30 8.0 84.4 0.7 0.4/1.9 0.4 3.9 36668- 3 300 1 0.3 30-50 30 27.7 68.6 1.5 0.6/0.7 - 1.0 91* 36668- 0.1 75 50 2.4 30-40 4 35.9 62.7 - 0.2/0.5 - 0.7 92*** 15 25.8 71.1 0.07 0.4/1.1 0.1 1.1 36845- - 75 50 2.4 30-40 24 38.4 60.2 - 0.1/0.5 - 0.7 1*** 36845- 0.5 60 65 1.2 30-40 10 72.9 19.4 0.3 - - 0.4 3*** 36845- 2 160 50 2.5 0-5 4 18.0 80.0 0.6 0.3/0.6 - 0.3 7**** 7 6.3 91.1 0.6 0.3/1.3 - 0.5 * Br/FBA mol. ratio 1.2<BR> ** FBA - 20 g (0.16 mol); Br2/FBA mol. ratio - 0.7<BR> *** FBA - 40 g (0.32 mol); Br2/FBA mol. ratio - 0.7<BR> **** FBA - 40 g (0.32 mol); Br2/FBA mol. ratio - 0.6 Table III<BR> Bromination of 4-fluorobenzaldehyde (FBA) in oleum -<BR> (FBA - 40 g; Br2/FBA mol. ratio - 0.59; GC analysis of the reaction mixture before wo@ Exp. lodine oleum SO3/ Temp. Time FBA BFBA IFBA DBFBA1 TBFBA PBFB No w/wFBA weight concr. FBA DBFBA2 g g % SO3 mol ratio °C hr %GC %GC %GC %GC %GC %GC 36668- 21 3 290 25 2.8 30-40 13 0.5 89.5 1.4 1.3/3.6 0.9 1.0 25 5 290 18 2.0 65-70 16 2.4 85.0 1.8 1.0/3.3 0.6 6.0 35* 5 380 30 1.4 50 12 27.7 68.6 1.5 0.6/0.7 - 1.0 38* 5 200 65 1.6 50 8 39.3 56.0 0.8 0.7/1.8 - 0.8 48 3 120 65 3.0 50 2 - 72.1 1.5 2.5/8.1 6.7 3.5 49** 3 120 65 3.0 30-40 2.5 3.3 90.1 3.2 0.8/1.5 - 0.4 51 5 300 15 1.7 50 8.5 21.7 72.8 3.2 0.1/0.9 - 1.4 53 5 300 15 1.7 100 3.5 6.4 82.0 2.3 1.3/3.4 0.9 3.5 63** 2 120 50 2.3 30-40 7 3.4 90.8 1.1 1.0/2.4 0.4 0.9 65 1 120 50 2.3 30-40 2.5 0.5 92.3 1.2 1.2/3.7 0.5 0.5 3.0 - 88.0 0.9 2.0/6.2 2.3 0.7 67*** 0.5 100 65 2.5 30-40 4 1.5 92.2 0.9 1.2/2.6 0.3 1.0 * 124 g FBA<BR> ** Br2/FBA mol. ratio - 0.5<BR> *** Br2/FBA mol. ratio - 0.55 Example 2 Preparation of 3-bromo-4-chlorobenzaldehyde (BCBA) bv the bromination of 4-chlorobenzaldehyde (CBA) in oleum.

Into a 250 ml flask equipped with a mechanical stirrer, a condenser, a thermometer and a dropping funnel, were introduced at room temperature and with a stirring, 65 g oleum (65% free SOs), 15 g H2SO4 (98%) and 0.2 g iodine. 20 g (0.14 mole) CBA was added dropwise over one hour at a temperature in the range of 30-40°C, then about 13 g bromine was added dropwise over 2 hours. The Br2/FBA molar ratio was 0.60. Stirring was continued for an additional 2 hours at 30-40°C. Samples were removed during the bromination to check the reaction conversion by GC analysis. After completion of the reaction, 100 g water was added carefully and then 120 g dichloroethane. After separation of the lower organic layer, the aqueous acidic phase was extracted again with 120 g dichloroethane. The combined organic layers were washed with 100 g water. After solvent stripping, 28 g crude BCBA, with a purity of ca. 85% (GC, area), was obtained. The yield was about 78%.

Example 3 Bromination of benzaldehyde The bromination of benzaldehyde was carried out to obtain 3- bromobenzaldehyde or 3,4-dibromobenzaldehyde. The results are presented in Table IV.

Table IV:<BR> Bromination of benzaldehyde in oleum (BA - 20 g, 0.19 mole, Br2/BA mol. ratio - 0.6; I@<BR> g; oleum or H2SO4 - 100 g) Exp. No. Br2 oleum Temp. BA 3BBA 4BBA 3,4DBBA DBBA TBBA TeBBA 36668- % conc. °C %GC %GC %GC %GC %GC %GC %GC %SO3 1 50 20 20-25 75.5 15.8 2.3 1.8 1.1/0.4 0.2 - 75 49.0 28.0 7.3 8.5 5.1/2.0 0.3 - 100 37.9 32.1 5.2 15.8 2.9/3.4 1.1 - 2 75 97% 40 90 3.9 2.5 3.1 - - - H2SO4 3* 50 20 40 26.1 34.0 5.7 25.8 2.5/3.8 0.5 - 100 - - - 55.2 2.0/12.5 5.4/3.8 19.4 *Br2/BA mol. ratio - 1.2<BR> BA - Benzaldehyde<BR> 3BBA - 3-Bromobenzaldehyde<BR> 4BBA - 4-Bromobenzaldehyde<BR> DBBA - Dibromobenzaldehyde<BR> TBBA - Tribromobenzaldehyde<BR> TeBBA - Tetrabromobenzaldehyde The selectivity of the bromination in oleum (20% free S03) for 3BBA at 20- 25°C was only 32.1% (Exp. No. 36668-1), while bromination in H2SO4 (97%) at 40°C showed poor conversion (Exp. No. 36668-2). The experiment to 3,4- dibromobenzaldehyde (Exp. No. 36668-3) showed a selectivity-55.2%.

Example 4 Bromination of benzophenone in oleum Into a 250 ml flask equipped with a mechanical stirrer, a condenser, a thermometer and a dropping funnel, were introduced, at room temperature and with stirring, 75 g H2S04 (97%), 0.5 g iodine, 18.2 g benzophenone and 70 g oleum (65% free S03). The temperature rose to ca. 75°C. The flask was stirred for 0.5 hr, the temperature dropped to ca. 30°C, then 23 g (0.14 mole) bromine was added dropwise over two hours. Stirring was continued for an additional hour. Samples were removed during the bromination to check the reaction conversion by GC analysis.

The main components of the reaction mixture were identified by GC/MS analysis, and the results are presented in Table V.

Table V<BR> Bromination of benzophenone in oleum.<BR> <P>Benzophenone - 18.2 g (0.1 mole); Oleum (65% free SO3) - 70 g; H2SO4 (97% - 75 g) Exp. Time Bromine Temp. BP 3BBP 3,4'DBBP 3,3'DBBP BIBP TBBP TeBBP No. hr °C %GC %GC %GC %GC %GC %GC %GC 36668- g mmole 41 0.5 9 56 22-40 12.6 67.3 3.3 11.0 0.8 2.4 - 1.0 9 56 - 48.4 3.7 29.1 2.0 8.7 3.3 2.0 6 38 - 39.7 2.5 33.6 1.8 10.4 7.0 3.5 - 25.7 2.3 35.6 3.1 11.0 9.0 43 0.7 18 113 0-5 48.0 49.0 0.6 2.5 - - - 2.5 0-5 6.2 71.4 2.5 15.4 - 1.7 - 6.5 5 31 0-5 2.2 60.1 2.7 22.3 1.3 3.4 0.7 10.5 10 - 29.2 2.0 38.4 0.7 10.4 9.5 14.5 10 - 24.9 1.2 37.8 1.0 11.2 15.0 BP - Benzophenone<BR> 3BBP - 3-Bromobenzophenone<BR> 3,4DBBP - 3,4'-Dibromobenzophenone<BR> 3,3DBBP - 3,3'-Dibromobenzophenone<BR> BIBP - Bromoiodobenzophenone<BR> TBBP - Tribromobenzophenone<BR> TeBBP - Tetrabromobenzophenone As can be seen, this route is very attractive for the preparation of 3- bromobenzophenone, when the bromination is carried out at a low temperature (0-5°C) and with a deficiency of bromine.

The reaction mixtures of Exp. No. 36668-41 and Exp. No. 36668-43 were worked up and the obtained crude material was then distilled in vacuum to give 3BBP and 3,3'DBPP.

Their structures were confirmed by NMR.

Example 5 Chlorination of 4-fluorobenzaldehyde The preparation of 3-chloro-4-fluorobenzaldehyde (CFBA) by the chlorination of 4-fluorobenzaldehyde (FBA) in oleum was carried out as follows.

Into a 100 ml flask equipped with a mechanical stirrer, a condenser, a thermometer and a gas inlet device, were introduced, at room temperature and with stirring, 65 g oleum (65% free SOs), 15 g H2SO4 (98%) and 0.2 g iodine. 20 g (0.16 mole) FBA was added dropwise over 0.5 hour at a temperature in the range of 30-40°C, then gaseous chlorine from a lecture bottle was fed continuously at 40-50°C into the reactor over a period of 10 hours, while the excess chlorine evolved and was absorbed in an aqueous NaOH trap attached to the top of the condenser. Samples were removed during the chlorination, to check the reaction conversion by GC analysis.

After reaction completion, 100 g water was added carefully, and then 100 g dichloroethane. After separation of the lower organic layer, the aqueous acidic phase was extracted again with 50 g dichloroethane. The combined organic layers were washed with 100 g water. After solvent stripping, 19.4 g crude CFBA with a purity of ca. 83% (GC, area) was obtained. The yield was about 63%.

Example 6 The preparation of FPBA by the bromination of FBA in oleum, followed by acetalization, Ullmann condensation and hydrolysis, without any intermediate purification was carried out. The overall yield was about 46%.

The various reaction steps and intermediate results are described below: ComparativePreparation Acetalization of purified 3-bromo-4-fluorobenzaldehyde (BFBA) with ethylene glycol was carried out under an atmosphere of nitrogen, using 85% H3PO4 as the catalyst. The reaction was complete after 2-3 hours.

The reaction may also be carried out without an acid catalyst, and in this case, it was completed in 5 hours. The results of the experiments on the acetalization of distilled BFBA are presented in Table VI.

Table VI<BR> Acetalization of distilled BFBA with ethylene glycol<BR> (BFBA - 32.8 g, 0.16 mole, Catalyst - 1 g of 85% H3PO4 Exp. No. EG Solvent Solvent Temp. Time BFBA BFPD IFPD DBFPD1 13680- g(mole) quantity DBFPD2 ml °C hr %GC %GC %GC %GC 2-1* 20.5(0.33) EDC 30 100 1 18.8 80.1 0.5 0.2/0.2 2 2.7 96.2 0.6 0.2/0.2 3 0.8 98.1 0.7 0.2/0.2 2-2* 20.5(0.33) Xylene 20 100 2 0.3 98.6 0.7 0.2/0.2 2-4* 20.5(0.33) Xylene 20 + 100 1 5.1 93.7 0.6 0.2/0.2 3 H2O 2 0.6 97.7 0.6 0.2/0.2 3 0.5 98.5 0.6 0.2/0.2 2-5* 20.5(0.33) Xylene 20 + 100 1 19.5 79.8 0.4 0.15/0.13 3 H2SO4 3 13.3 85.5 0.4 0.15/0.13 (70%) 4.5 18.3 78.4 0.4 0.14/0.13 2-6* 11(0.18) Xylene 20 100 1 12.6 86.4 0.4 0.1/0.2 3 7.5 91.6 0.5 0.1/0.2 6 5.7 93.4 0.5 0.1/0.3 2-9** 20.5(0.33) Toluene 20 100 1 14.3 85.7 - - 3 1.3 98.7 4 0.3 99.7 2-10** 20.5(0.33) Xylene 20 100 1 32.8 77.2 - - 3 2.4 97.6 5 0.2 99.8 *BFBA - 99.0%; IFBA - 0.6%; DBFBA - 0.4%<BR> **BFBA - 99.9<BR> Exp. No. 13680-2-10 without catalyst Step A Acetalization of crude 2-bromo-4-fluorobenzaldehyde (BFBA) (without distillation) with ethylene glycol at a temperature of 100°C.

Crude BFBA was obtained by bromination of 0.16 mol FBA. An additional amount of crude BFBA was obtained by extraction of the aqueous phase with 36 ml of EDC. A further batch of crude BFBA was obtained by the bromination of 1 mole FBA. Extraction of the aqueous phase was carried out with 100-140 ml xylene. The crude BFBA was acetalized as described above.

In all of these experiments (Table VII), no additional catalyst or solvent was added in the acetalization stage.

Table VII<BR> Acetalization of crude BFBA (without distillation) with ethylene glycol (Temp: 100°C) Exp. No. EG Solvent Solvent Time BFBA FPD BFPD IFPD DBFPD1 13680- g (mole) quantity DBFPD2 ml hr %GC %GC %GC %GC %GC 2-8 23.8(0.38) EDC 36 1.5 0.5 3.3 88.2 1.3 0.8/2.6 3.0 0.5 2.8 8.4 1.3 0.8/2.6 2-11 124 (2) Xylene 100 2 5.2 0.6 82.3 1.7 1.1/3.9 4 - 0.6 87.9 1.7 1.0/3.6 2-13 124 (2) Xylene 140 4 3.0 1.0 88.1 1.1 0.9/2.5 2-14* 248 (4) - - 3 0.5 0.5 90.3 2.4 1.0/2.8 *without solvent, under vacuum.

Step B Preparation of 4-fluoro-3-phenoxvphenvldioxolane (FPPD) Experiments were carried out on the Ullman coupling of 3-bromo-4- fluorophenyl dioxolane with potassium phenolate to yield 4-fluoro-3- phenoxyphenyl dioxolane. CuCl, Cu, CuO and Cu2S04 were used as catalysts.

Several different solvents and homogenizers were tested. The results of the above experiments are presented in Table VIII.

Table VIII<BR> Preparation of 4-fluoro-3-phenoxyphenyl dioxolane (FPPD): (BFPD - 20 g, 0.08 mole@<BR> molar ratio - 1.15; KOH/NaOH molar ratio - 7; PhOH/(KOH+NaOH) molar rati@ Exp. Solvent Catalyst Catalyst/ Temp Time FPD BFPD FPPD BPPD DPPD No. BFPD 114- mol% °C hr %GC %GC %GC %GC %GC 125-1 diglyme CuCl 3.5 140 3.5 8.2 10.8 76.5 1.4 - 9.8 ml 5.5 8.8 3.9 80.0 1.1 2.0 7.0 10.7 2.5 80.6 0.9 2.6 125-2 diglyme Cu 4.0 140 2.0 0.3 87.9 6.7 3.2 0.7 9.8 ml 160 4.0 12.1 0.7 76.1 - 7.3 125-3 diglyme CuSO4 2.0 140 1.2 1.8 56.6 31.9 5.0 0.2 9.8 ml 5.0 4.3 21.6 68.7 3.8 0.9 7.0 4.9 14.4 74.9 4.1 1.3 9.0 4.9 11.4 76.7 4.1 1.6 11.0 4.5 10.9 78.2 4.2 1.6 125-4 diglyme CuCl 2.0 140 1 2.8 45.0 45.9 4.4 0.4 9.8 ml 5 8.1 4.1 78.7 2.8 3.3 6 8.8 3.7 78.1 2.3 4.7 7 10.0 2.8 77.4 1.9 4.7 125-5* diglyme CuCl 3.5 120- 3 8.6 14.0 72.7 1.5 1.7 9.8 ml 140 7 16.1 2.5 74.2 - 4.3 125-7 diglyme CuCl 3.5 120- 1 4.2 49.0 42.7 1.1 0.5 9.8 ml 130 3 5.9 25.0 65.8 2.1 0.4 5 10.0 11.3 74.9 1.7 0.8 7 10.6 2.6 82.1 1.1 2.8 125-8 diglyme CuSO4 3.5 140 1 4.6 47.2 44.8 2.8 - 9.8 ml 3 6.9 16.7 69.2 5.0 1.6 5 8.1 9.0 75.4 4.7 2.7 7 8.4 7.1 76.6 4.4 3.1 Table VIII (Cont'd) Exp. Solvent Catalyst Catalyst/ Temp Time FPD BFPD FPPD BPPD DPPD No. BFPD 114- mol% °C hr %GC %GC %GC %GC %GC 125-9 phenol CuCl 3.5 125- 1 9.2 44.0 44.1 1.2 0.2 7.5 g 130 2 16.1 27.5 54.5 0.9 0.5 3 22.6 11.9 62.4 0.6 1.8 4.5 24.1 7.3 64.2 0.5 2.5 di (ethylenglycol) methyle-ether.

Table VIII (Cont'd) Exp. Solvent atalyst Catalyst/Temp Time FPD BFPD FPPD BPPD DPPD No. BFPD 114-mol% °C hr % GC % GC % GC % GC % GC 125-toluene CuCl 3.5 120- 1 2.9 72.9 22.8 0.3 - 10 7.3 ml 140 3 7. 5 33. 5 54. 8 0.3 2.0 4 9. 3 23. 9 61. 2 0.2 3.2 7 14. 2 8. 9 68. 0 0.2 4.3 125-NMP CuCl 3.5 120-1 7. 6 35. 1 52. 7 3.2 0.3 11 6.6 ml 130 2 10. 9 13. 3 70. 9 3.0 0.8 3 13. 0 5. 4 76. 0 2.5 1.5 4 14. 4 3. 5 76. 9 2.0 1.8 5 14. 6 2. 5 77. 2 2.0 2.3 125-PEG CuCl 3.5 120-1 8. 0 54. 1 36. 8 0. 4- 12 600 140 3 10.7 32.5 54. 9 0. 7- 20.865.50.8511.5 0.2 2 g 4.978.00.61.51013.1 125-PEG CuCl 3.5 120-1 3. 9 48. 0 43. 0 3.1 0.2 13 600 130 4 6. 9 16. 9 70. 9 2.9 0.9 2 g 6 7.5 14.4 72. 7 2.6 1.2 8 9. 0 11. 9 73. 5 2.9 1.3 125-NMP CuCl 3.5 120-19. 646. 741. 20. 6 14 2 ml 130 2 12. 1 30. 4 56. 7 0. 9 125-125-diglyme CuCl 8 5.268.925.10.5-1 15 9.8 ml 130 3 7.2 51.6 38.3 - 5 8. 8 30. 0 59. 3 1. 3- 8 14.9 2.9 78.2 0.5 1.2 125-diglyme CuO 3.5 110-1 0. 5 91. 0 5 ; 0 0.6 0.2 16 9.8 ml 140 3 1. 7 69. 8 24. 4 2.5 0.2 5 2.8 49.4 41.2 4.2 0.3 7 3.6 32. 9 56.8 5.36 0. 125-diglyme CuCl 3.5 120-3 6. 7 53. 6 38. 1 0.2 17** 9.8 ml 130 7 11. 0 6. 2 80. 2 0. 3 *BFBA was introduced gradually.

**Phenolate was introduced gradually.

***PEG = POLYETHYLENGLYCOL ****NMP = N-METHYLPYRROLIDONE The hydrolysis of the product of the condensation is a straightforward procedure, well known in the art, and it is therefore not exemplified, for the sake of brevity. All the above descriptions and examples have been provided for the purpose of illustration, and are not intended to limit the invention in any way. Many modifications can be carried out in the process of the invention: for instance, various catalysts, solvents and reagents can be used, at different reaction conditions, all without exceeding the scope of the invention.