The present invention relates to a method for cleaving arylethers. This method is used in processes for preparing 4,6-diaminoresorcinol, a monomer used in preparing polybenzoxazoles (PBO). Although there are a number of known methods for preparing 4,6-diaminoresorcinol, there continues to be a need to find more efficient and cost effective routes to obtain 4,6-diaminoresorcinol.

One known method involves synthesizing the monomer from 1 ,2,3- -trichlorobenzene as described in U.S. Patent No. 4,766,244 issued to Lysenko. However, 1,2,3-trichlorobenzene has limited availability.

Another method for preparing 4,6-diaminoresorcinol involves treating 1,3-dichloro-4,6-dinitrobenzene with base to form 4,6-dinitroresorcinol. Although A 4,6-dinitroresorcinol may be reduced to form 4,6-diaminoresorcinol, the product recovery is prohibitively low for commercial value.

In yet another method, the appropriate arylether such as di-arylmethoxy- dinitrobenzene can be cleaved to produce 4,6-diaminoresorcinol. U.S. Patent No. 5,072,053, issued to Blank et al., describes cleaving arylethers by converting di-arylmethoxy- dinitrobenzenes to 4,6-diaminoresorcinol by catalytic reduction using a platinum metal supported catalyst, which cleaves the diethers and reduces the nitro groups to amines.

However, this described method also produces toluene as an unwanted by-product which must be removed or converted back to benzyl alcohol for recycle.

Other known methods for cleaving arylethers are described in Protective Groups in Organic Chemistry by Theodora W. Greene, pp. 88-100, 1981 , J. Wiley & Sons using, for example, hydrobromic acid or hydroiodic acid. Unfortunately, large amounts of hydrobromic acid or hydroiodic acid are required. In addition, when hydroiodic acid is used to cleave dinitroarylethers, such as methyl and benzyldinitroarylethers, the reaction is complicated in that the amines formed from the reduction of the nitro groups with iodide are subsequently alkylated by the alkyl iodide present. This reaction produces unwanted by-products, particularly when the desired product is 4,6-diamino-resorcinol used in benzoxazole polymerization.

In yet another method, as described in an article by Bernard et. al., in Synthesis, April 1989, pp. 287-289, alkyl arylethers are cleaved using lithium chloride in an N,N- -dimethylformamide solvent. However, this method requires a three-fold excess of lithium chloride which gives added expense to the method.

Accordingly, it remains highly desirable to provide a method for cleaving arylethers which does not have the disadvantages of the prior art.

Accordingly, in one aspect, the present invention is a method for cleaving arylethers comprising the step of contacting an arylether with an amide hydrohalide salt at conditions sufficient to cleave the ether group(s) of the arylether and form a phenol or substituted phenol. In a second aspect, the present invention is a method for preparing

4,6-diaminoresorcinol comprising the steps of contacting a mono or diether of 4,6-dinitroresorcinol with an amide hydrohalide salt to form 4,6-dinitroresorcinol; and hydrogenating 4,6-dinitroresorcinol to form 4,6-diaminoresorcinol.

In one preferred embodiment for the preparation of arylethers used in preparing 4,6-diaminoresorcinol, a monoether of 4,6-dinitroresorcinol is prepared by contacting

1 ,3-dichloro-4,6-di nitrobenzene with an aqueous alcohol in the presence of hydroxide base. In a second preferred embodiment, a monoether of 4,6-dinitro-resorcinol is prepared by contacting 2,4-dinitrochlorobenzene with a hydroperoxide in the presence of an anhydrous alkali metal hydroxide, and an alkyl alcohol or benzyl alcohol, to form a 5-alkoxy-2,4- -dinitrophenol or a 5-benzyloxy-2,4-dinitrophenol. In yet another preferred embodiment, a diether of 4,6-dinitroresorcinol is prepared by contacting 1 ,3-dichloro-4,6-dinitro-benzene with i) a hydroxy-containing compound in the presence of hydroxide base or ii) an alkanolic metal alkoxide.

Using the method of the present invention, arylethers can be cleaved without the need for large amounts of hydrobromic acid, hydroiodic acid or lithium chloride and without the formation of unwanted by-products. The method of the present invention is particularly useful for the preparation of 4,6-diaminoresorcinol, a monomer used for making polybenzoxazoles (PBO).

The term arylether as used in the present invention refers to any compound containing an aryl group which has been substituted by at least one ether group, including mono and diethers, such that upon cleavage of the ether groups, a phenol or substituted phenol is formed. The arylethers used in the present invention may be any arylether which is stable under the reaction conditions and does not form undesirable by- -products which would be detrimental to the reaction. Arylethers appropriate for the process of the present invention include but are not limited to arylethers of the formula:

(A)n (0 - CH ₂ - R) _x

wherein R is hydrogen, C^C _g alkyl, cycloalkyl, phenyl or substituted phenyl, CH = CH or any organic moiety which will not be detrimental to the formation of the final product; each A is independently NO., hydroxy, halo, or methoxy; n is an integer from 0 to 5; and x is 1 or 2.

The preferred arylethers advantageously employed in the present invention include alkyl arylethers, branched alkyl arylethers, cycloalkyl arylethers, allyl arylethers and benzyl arylethers. Preferred arylethers correspond to the formula:

wherein R is hydrogen, C _t -C ₆ alkyl, C3-C6 cycloalkyl, phenyl or substituted phenyl, or CH = CH ₂ ; each A is independently NO., hydroxy, halo, or methoxy; n is an integer from 0 to 5; and x is 1 or 2. Preferably R is methyl, ethyl, allyl, hydrogen, phenyl or phenyl substituted with a halogen or an electron withdrawing group. More preferably R is phenyl, or hydrogen. Most preferably, R is hydrogen. Preferably, n is 0, 2 or 3 and each A is independently NO., hydroxy, halo, or methoxy. More preferably n is 3 and each A is independently N0 ₂ , hydroxy, halo, or methoxy. Most preferably, n is 3, two of the A substituents are NO. and the third A is hydroxy or methoxy.

The arylethers used can be prepared by techniques well-known in the art for preparing such ethers. In one aspect of the present invention, 4,6-diaminoresorcinol is prepared. In one method of the present invention 4,6-diaminoresorcinol is prepared from the monoether of 4,6-dinitroresorcinol. The monoether of 4,6-dinitroresorcinol is advantageously prepared in one embodiment by contacting 1 ,3-dichloro-4,6-dinitro-benzene with an aqueous alkyl alcohol in the presence of hydroxide base, preferably sodium hydroxide, under conditions sufficient to produce a monoether, specifically 5-alkoxy-2,4-dinitrophenol. Similarly, 1,2,3-trichloro-4,6- -di nitrobenzene may also be converted to 6-chloro-5-alkoxy-2,4-dinitrophenol underthe same conditions. In another method 4,6-diaminoresorcinol is prepared from the diether of 4,6- -dinitroresorcinol. A diether of 4,6-dinitroresorcinol can be similarly prepared by contacting 1 ,3-dichloro-4,6-di nitrobenzene or 1 ,2,3-trichloro-4,6-dinitrobenzene with a hydroxy- -containing compound in the presence of hydroxide base, (greater amounts of hydroxy- -containing compound can be employed than in preparing the monoether). Alternatively, the diether can be formed by contacting 1 ,3-dichloro-4,6-dinitrobenzene or 1 ,2,3-trichloro-4,6- -dinitrobenzene with an alkanolic sodium alkoxide, preferably methanolic sodium methoxide, under conditions sufficient to produce a diether, specifically 1,3-dimethoxy-4,6-dinitrobenzene or 1,3-dimethoxy-2-chloro-4,6-dinitrobenzene. 1,3-Dichloro-4,6-di nitrobenzene can be prepared by the dinitration of m-dichlorobenzene as in Boyer and Buriks, Organic Synthesis Collective Vol. 5, p. 1067, John Wiley & Sons Inc., New York 1973 and 1 ,2,3-trichlorobenzene may be dinitrated under equivalent conditions.

The starting materials appropriate for preparing the arylethers used in the present invention include any hydroxy-containing compound which will form an ether when reacted with an aryl compound. The preferred hydroxy-containing compounds are benzyl alcohols, allyl alcohols, cycloalkyl alcohols, and branched- or straight-chain C.-C. alkyl alcohols, such as methanol, ethanol and propanol. More preferred are benzyl alcohol and alkyl alcohols, such as methanol and ethanol, wherein the most preferred is methanol or benzyl alcohol.

The alkanolic metal alkoxide which can be employed in preparing the dinitroarylether is an alkanolic solution containing an alkali metal alkoxide which can be prepared by dissolving an alkali metal in an alkanol. The alkanol may be a C,-C _; alkanol, is preferably C.-Q ₃ alkanol and is most preferably methanol. The metal may be any alkali metal and is most preferably sodium. The solution may contain any effective amount of alkali metal but it preferably contains from about 20 to about 40, most preferably about 25 weight percent, said weight percent being based on the total weight of the solution.

In a second embodiment, the monoether of 4,6-dinitroresorcinol is advantageously prepared by contacting 1-chloro-2,4-dinitrobenzenewith a hydroperoxide in the presence of an anhydrous alkali metal hydroxide, (as described in Makosza and Sienkiewicz, Journal of Organic Chemistry, Vol. 55 No. 17, August 17, 1990, " Hydroxylation of Nitroarenes with Alkyl Hydroperoxide Anions via Vicarious Nucleophilic Substitution of Hydrogen"), and further reacted with an alkyl or benzyl alcohol to form a 5-alkoxy- or a 5-benzyloxy-2,4- -dinitrophenol.

The hydroperoxide may be any tertiary alkyl or aralkyl hydroperoxide. The term aralkyl refers to a radical in which an alkyl H atom is substituted by an aryl group. Preferred hydroperoxides are cumyl, tert-butyl, and neopentyl hydroperoxides. More preferred are cumene hydroperoxide and tert-butyl hydroperoxide. Most preferred is cumene hydroperoxide.

The alkali metal hydroxide is preferably sodium hydroxide, potassium hydroxide, lithium hydroxide or cesium hydroxide. More preferred is sodium hydroxide or potassium hydroxide, wherein the most preferred is sodium hydroxide.

In the practice of the present invention, the arylethers are cleaved using an amide hydrohalide salt. While the amide hydrohalide salt most advantageously employed in the practice of the present invention will depend on a number of different factors, including the desired product and the conditions of reaction, in general, the preferred amide hydrohalide salts used in the method of the present invention are tert-amide hydrochloride, hydrobromide or hydroiodide salts. A tert-amide is any compound containing a nitrogen atom bonded to three carbon atoms wherein one of the carbon atoms is part of a carbonyl group. The preferred tert-amide hydrohalide salts are the hydrohalide salts of N,N-dimethylformamide (DMF), cyclohexylpyrrolidinone, hexamethylpyrrolidinone, hexamethylphosphoramide, N,N-dimethylacetamide (DMAC) and N-methylpyrrolidinone (NMP). More preferred are the

hydrochloride salts of N,N-dimethylformamide, cyclohexylpyrrolidinone, hexamethylpyrrolidinone, hexamethylphosphoramide, N,N-dimethylacetamide and N-methylpyrrolidinone. Most preferred is the hydrochloride salt of N,N-dimethyl-acetamide. Methods for preparing amide hydrohalide salts are described in "Pyrrolidinecarboxaldehyde Hydrohalide Catalyzed Halogenations of Aliphatic Aldehydes," Synth. Commun., 15 (11), pp. 977-84, by Pews and Lysenko. In general, the amide hydrohalide salt is prepared from the corresponding amide by saturating the amide with an appropriate dry hydrogen halide gas. In most cases the salts are solids and may be isolated by filtration and stored or prepared and used in situ from the addition of the appropriate amount of hydrogen halide.

The arylether and the amide hydrohalide salt are used in amounts and at conditions sufficient to cleave the arylether group(s) and produce the desired phenol. While the relative amounts of the arylether and the amide hydrohalide salt most advantageously used can vary depending on a number of factors, including the specific arylether and amide hydrohalide salt employed, and the reaction conditions, it is generally preferable to use at least a stoichiometric amount and less than 1.5 equivalents of the hydrohalide salt per equivalent of the arylether. More preferably, the amide hydrohalide salt is used in an amount from 1.0 to 1.2 equivalents per equivalent of arylether. Most preferably, the amide hydrohalide salt and arylether are employed in stoichiometric amounts. A stoichiometric amount of amide hydrohalide salt refers to the amount of amide hydrohalide salt needed to react with the reactive site or sites of the arylether, without excess, to produce the desired phenol.

Although the reaction may be conducted without a solvent under certain conditions, it is most prefer-ably conducted in a solvent for the arylether, the amide hydrohalide salt and their reaction product. Any solvent for the arylether, amide hydrohalide salt, and their reaction product which does not significantly and adversely affect the reaction may be employed. Any polar aprotic solvent is advantageously employed in the method of the present invention. The preferred solvents are tert-amides. More preferred is a tert-amide cor¬ responding to the amide hydrohalide salt, for example, N,N-dimethylacetamide is used as the solvent when N,N-dimethylacetamide HCI salt is used in the reaction. Most preferred amide solvents include N,N-dimethyl-formamide, cyclohexylpyrrolidinone, hexamethylpyrrol-idinone, hexamethylphosphoramide, N,N-dimethylacetamide and N-methylpyrrolidinone. More preferred amide solvents include N,N-dimethylformamide, N,N-dimethyl-acetamide and N-methylpyrrolidinone.

The temperature and pressure at which the cleavage reaction is most advantageously conducted is dependent on many factors including the specific reactants and the desired reaction product. The cleavage reaction can be carried out at any temperature which is sufficient for the cleavage reaction to occur. Preferably, the reaction is carried out at a temperature from 75°C to 180°C. More preferably, the reaction is conducted at temperatures

from 120°Cto 140°C and most preferably at a temperature of 130°C. At these temperatures, the reaction generally requires from 1 hour to 30 hours. More preferably, the reaction is conducted from 2 hours to 24 hours and most preferably from 3 hours to 20 hours.

The pressures employed in the methods of the present invention will depend on many factors including the temperature, specific reactants and the product desired. Any pressure at which the cleavage reaction will occur is acceptable. The preferred method uses atmospheric pressure.

Following the cleavage reaction, the reaction product can be further reacted or recovered using conventional techniques such as removing the solvent from the reaction mixture, washing with HCI, extracting with ethyl acetate, drying and concentrating. In the preparation of 4,6-diaminoresorcinol by the method of the present invention, the cleaved reaction product is 4,6-dinitroresorcinol. 4,6-Dinitroresorcinol isthen reduced and recovered most advantageously as a hydro-chloride salt of 4,6-diaminoresorcinol. Hydrogenation of 4,6-dinitroresorcinol is well-known in the art and described in U.S. Patent No. 4,912,246 issued to Lysenko et. al. Any hydrogenation process which will reduce nitro groups to amino groups can be used in the process of the present invention. In a preferred method, 4,6-dinitroresorcinol is reduced to 4,6-diaminoresorcinol by contacting it with a reducing agent, such as hydrogen gas in the presence of a reduction catalyst, such as palladium on carbon. The following examples are set forth to illustrate the present invention and should not be construed to limit its scope. In the examples, all parts and percentages are by weight unless otherwise indicated. Preparing Ethers of Dinitroresorcinol Example 1 - Preparing 5-Methoxy-2,4-dinitrophenol from 1,3-Dichloro-4,6-dinitrobenzene:

A 1 -liter (L), round-bottom flask equipped with a mechanical stirrer and a reflux condenser was charged with 23.7 grams (g) of 1 ,3-dichloro-4,6-dinitrobenzene, 100 milliliters (mL) of methanol, 200 mL of water and 15 grams of sodium hydroxide and heated to approximately 65°C for 8 hours. The reaction mixture was then poured into 0°C aqueous hydrochloric acid, isolated by filtration and air-dried. The theoretical of 5-methoxy-2,4- -dinitrophenol yield was 21.4 g, and the dry weight yield was 20.5 g which gives an overall 95 percent yield.

Example 2 - Preparing 1 ,3-Dimethoxy-4,6-dinitrobenzene from 1 ,3-Dichloro-4,6- -dinitrobenzene:

A 1 -liter, 3-necked, round-bottomed flask was charged with 500 mL of methanol, 30 g of crushed potassium hydroxide, 75 mL of water, and 23.7 g (0.10 mole) of 1 ,3-dichloro- -4,6-dinitrobenzene. The reaction mixture was agitated and heated to 65°C for 8 hours and cooled to 25°C. The reaction mixture was then quenched with an excess of 0°C aqueous hydrochloric acid. The resulting pale yellow solid was isolated by filtration and air-dried to yield 20 g (90 percent yield) of 1 ,3-dimethoxy-4,6-dinitrobenzene. Example 3 - Preparing 5-Methoxy-2,4-dinitrophenol from 2,4-Dinitro-chlorobenzene: f ¹ OH _^ 0CHτ Hydroperoxide/MeOH Y^ _N \

&

N0 ₂ - N0 ₂ ^anh - ^Na0H ^ ^

N0 ₂ N0 ₂

20 g of NaOH powder was added to a 250 mL 3-necked flask equipped with a mechanical stirrer, CO. condenser, dropping funnel and thermowell. Approximately 100 to 125 mL of liquid NH ₃ were condensed into the reactor utilizing a dry ice bath. To the stirred slurry of powdered NaOH-NH. a solution of

1-chloro-2,4-dinitrobenzene (0.1 mol) and cumene hydroperoxide (0.1 mol) in 50 mL of methylene chloride was added dropwise over 1 hour maintaining the temperature at -30°C by the refluxing NH..

After the addition was completed, the reaction mixture was allowed to warm to -10°C to 0°C and 75 mL of methanol containing 0.1 to 2 g of sodium hypophosphite was added dropwise over 1 hour. The resulting solution was agitated at room temperature for 3 to 4 hours.

The reaction mixture which contained precipitated Na phenolic salts was diluted with water to dissolve the salts and transferred to a 1 -L separating funnel (to which a 500 mL solution of H ₂ 0 had been added) where the aqueous solution was extracted with CH.C1. (2x200 mL) to remove the cumene derivatives. After extraction, the aqueous phenate salt solution was slowly acidified with concentrated HC1 at a temperature of approximately 25°C or less to precipitate the desired 5-methoxy-2,4-dinitrophenol. The crude phenol (17 to 19 g) was

recrystallized from H ₂ 0-MeOH (50:50) to give the preferred product in 75 percent to 80 percent yield.

Example 4 - Preparing 5-Benzyloxy-2,4-dinitrophenol from 2,4-Dinitrochlorobenzene:

To a stirred slurry of powdered NaOH (20 g) in 125 mL of liquid NH ₃ (-33°C) contained in a 250 mL flask equipped with a mechanical stirrer, dropping funnel, thermometer and dry ice condenser, was added 1 -chloro-2,4-di nitrobenzene (20.2 g), and 20 g of 80 percent cumene hydroperoxide in 50 mL of methylene chloride. Afterthe addition was complete, the reaction mixture was allowed to warm to -10°C and benzyl alcohol (75 mL) was added dropwise. The methylene chloride was removed in vacuo and the mixture was stirred overnight at approximately 25°C. The reaction mixture was then transferred to a separatory funnel containing 250 mL of H.O and was extracted twice with 50:50 toluene:hexane (2x200 mL) to remove the unreacted benzyl alcohol and cumene residues. After acidification with concentrated HCI, the product was isolated by extraction in ethyl acetate. The organic extract was dried over MgS0 ₄ and evaporated. The residue was slurried in hot toluene (approximately 500 mL) and suction filtered through a small bed of silica to remove impurities. After evaporation of the toluene, the residue (approximately 12 g) was recrystallized from CH _j CI.-methanol to give a yellow solid, melting point (m.p.) 140°Cto 142°C. Preparation of 4,6-Dinitroresorcinol

Example 5

To a 100 mL round-bottom flask was added 2.14 g (10 mmol) of 5-methoxy-2,4- -dinitrophenol (MDNP) and 1.31 g (12 mmol) of DMF-HC1 in 30 mL of N,N-dimethyl-formamide (DMF). This mixture was stirred at 130°Cand monitored by High Pressure Liquid Chromatography (HPLC). After 8.5 hours essentially no MDNP was observed by HPLC. The reaction mixture was poured into lOO mL of 1 N HC1 , and extracted with ethyl acetate (EtOAc, 3x30 mL). The combined organics were washed with a single portion of 0.1 N HC1 , dried (Na.S0 ₄ ) and concentrated by rotary evaporation to give crude 4,6-dinitroresorcinol (DNR) as a

yellow solid (1.9 g, 95 percent yield): melting point (m. p.) 205°C to 210°C, 1 H NMR (CDC1 ₃ ) δ 1 1.03 (s _r 2H), 9.08 (s,1 H), 6.82 (s,1 H). Example 6

To a 100 mL round-bottom flask was added 2.50 g (12 mmol) of MDNP and 3.25 g (24 mmol) of NMP-HCI in 30 mL of N-methylpyrrolidinone (NMP). This mixture was stirred at 130°C and monitored by HPLC. After 20 hours essentially no MDNP was observed by HPLC. The reaction mixture was poured into 50 mL of 1 N HC1 , and extracted with EtOAc (2x50 mL). The combined organics washed with a single portion of 0.3 N HC1 , dried (Na.S0 ₄ ) and concentrated by rotary evaporation to give 4,6-dinitro-resorcinol (DNR) as a yellow solid (3.1 g, 130 percent yield). ¹ H NMR showed the product to contain a significant portion of NMP. Example 7

To a 100 mL round-bottom flask was added 4.00 g (19 mmol) of MDNP and 2.89 g (23 mmol) of DMAC-HC1 in 15 mL of N,N-dimethylacetamide (DMAC). This mixture was stirred at 130°C and monitored by HPLC. After 6.5 hours essentially no MDNP was observed by HPLC. The reaction mixture was poured into 160 mL of 1 N HC1 , and extracted with EtOAc (3x75 mL). The combined organics are washed with 0.3 N HC1 , dried (Na ₂ S0 ₄ ) and concentrated by rotary evaporation to give 4,6-dinitroresorcinol (DNR) as a yellow solid (3.5 g, 92 percent yield). Example 8

A 100 mL, 3-necked, round-bottom flask was charged with 30 mL of N-methylpyrrolidinone, 2.6 g (0.02 mole) of 1 ,3-dimethoxy-4,6-dinitrobenzene. The resulting solution was heated to 130°C for 2 to 3 hours. The reaction mixture was then cooled and poured into an excess of dilute hydrochloric acid. The resulting solid was isolated by filtration to yield 1.9 g (95 percent yield) of 4,6-dinitroresorcinol.

Example 9 - Preparation of 4,6-Diaminoresorcinol Dihydrochloride

A 1-L Hastalloy C autoclave, equipped with a gas dispersion turbine, sampling port, thermowell, and a cooling coil was charged with 50.0 g (0.25 mole) of 4,6-dinitroresorcinol, 380 g of n-propanol, 100 g of water, and 19.0 g of ammonium acetate. An aqueous slurry of 2.5 g of 10 percent Pd/C catalyst, was added and the reactor was sealed and purged with nitrogen. Hydrogen gas was charged to the reactor, and the pressure was cycled between 50 and 80 psig while maintaining the temperature of the reaction between about 50°C to about 55°C. The progress of the reaction was monitored by hydrogen uptake. When no further hydrogen uptake was observed, the reactor was cooled to approximately 25°C and 300 mL of concentrated HC1, containing 1.5 g stannous chloride di hydrate, was added to the black reaction mixture. The resultant gray solid was isolated by filtration and air-dried to yield 57.0 g of the crude dihydrochloride salt of the diaminoresorcinol which also contained the catalyst as an impurity. Purification of 4,6-Diaminoresorcinol Dihydrochloride The crude diaminoresorcinol (57.0 g), from Step A, containing the Pd/C catalyst, was dissolved in 400 g of 6 percent aqueous HC1 at 80°C. The catalyst was removed by filtration. An additional 50.0 g of concentrated HC1 containing 1.5 g of stannous chloride dihydrate was added to the diaminoresorcinol mixture along with 5.0 g of activated carbon. The solution was heated at reflux for 15 minutes and then the carbon was removed by filtration. The filtrate was cooled to 0°C to allow crystallization of the product. The resulting white precipitate was isolated by filtration under a purge of dry nitrogen. This filter cake was then dried in vacuo at 40°C to a constant weight to yield 48.7 g of essentially pure (99.8 percent) 4,6-diaminoresorcinol dihydrochloride having a m.p. of >300°C. Elemental Anal, calc'd for C-H ₁₀ C1 ₂ N.0_ (213.0643): C, 33.82; H, 4.73; C1 , 33.28; N, 13.15; 0, 15.02, found: C, 33.6; H, 4.64; N, 13.20.

Η NMR. DMSO d. tøpm); 6.95 (1 H,s), 7.48 (1 H,s), 9.56 (b.s.), 10.5 (b.s). ¹³ C NMR, DMSO d, (ppm); 103.69, 109.87, 1 19.48, 151.25.