Process and intermediates for the preparation of certain nematicidal sulfonamides

Abstract

The present invention provides a method for preparing a compound of Formula C, Formula D, or Formula F: ##STR00001## wherein each R.sup.1, R.sup.2, and R.sup.3 is independently H, SF.sub.5, N(C.sub.1-C.sub.8 alkyl)(C.sub.1-C.sub.8 alkyl), C(═S)N(C.sub.1-C.sub.8 alkyl)(C.sub.1-C.sub.8 alkyl), SO.sub.2N(C.sub.1-C.sub.8 alkyl)(C.sub.1-C.sub.8 alkyl), OSO.sub.2(C.sub.1-C.sub.8 alkyl), OSO.sub.2N(C.sub.1-C.sub.8 alkyl)(C.sub.1-C.sub.8 alkyl), N(C.sub.1-C.sub.8 alkyl)SO.sub.2(C.sub.1-C.sub.8 alkyl), or C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 haloalkyl, C.sub.2-C.sub.8 alkenyl, C.sub.2-C.sub.8 alkynyl, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10 halocycloalkyl, C.sub.4-C.sub.10 alkylcycloalkyl, C.sub.4-C.sub.10 cycloalkylalkyl, C.sub.6-C.sub.14 cycloalkylcycloalkyl, C.sub.5-C.sub.10 alkylcycloalkylalkyl, C.sub.3-C.sub.8 cycloalkenyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 haloalkoxy, C.sub.3-C.sub.8 cycloalkoxy, C.sub.3-C.sub.8 halocycloalkoxy, C.sub.4-C.sub.10 cycloalkylalkoxy, C.sub.2-C.sub.8 alkenyloxy, C.sub.2-C.sub.8 alkynyloxy, C.sub.1-C.sub.8 alkylthio, C.sub.1-C.sub.8 alkylsulfinyl, C.sub.1-C.sub.8 alkylsulfonyl, C.sub.3-C.sub.8 cycloalkylthio, C.sub.3-C.sub.8 cycloalkylsulfinyl, C.sub.3-C.sub.8 cycloalkylsulfonyl, C.sub.4-C.sub.10 cycloalkylalkylthio, C.sub.4-C.sub.10 cycloalkylalkylsulfinyl, C.sub.4-C.sub.10 cycloalkylalkylsulfonyl, C.sub.2-C.sub.8 alkenylthio, C.sub.2-C.sub.8 alkenylsulfinyl, C.sub.2-C.sub.8 alkenylsulfonyl, C.sub.2-C.sub.8 alkynylthio, C.sub.2-C.sub.8 alkynylsulfinyl, C.sub.2-C.sub.8 alkynylsulfonyl, or phenyl; or two of R.sup.1, R.sup.2, and R.sup.3 on adjacent ring atoms may be taken together to form a 5- to 7-membered carbocyclic or heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2 O, up to 2 S, and up to 3 N, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S) and such ring is optionally substituted with up to 3 substituents independently selected from the group consisting of C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.2-C.sub.4 haloalkynyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.7 halocycloalkyl, C.sub.4-C.sub.8 alkylcycloalkyl, C.sub.4-C.sub.8 haloalkylcycloalkyl, C.sub.4-C.sub.8 cycloalkylalkyl, C.sub.4-C.sub.8 halocycloalkylalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 haloalkoxy, C.sub.2-C.sub.8 alkoxycarbonyl, C.sub.2-C.sub.6 haloalkoxycarbonyl, C.sub.2-C.sub.6 alkylcarbonyl and C.sub.2-C.sub.6 haloalkylcarbonyl; and M is an inorganic cation or organic cation.

Claims

1. A method of preparing a compound of Formula C: ##STR00038## wherein each R.sup.1, R.sup.2, and R.sup.3 is independently H, SF.sub.5, N(C.sub.1-C.sub.8 alkyl)(C.sub.1-C.sub.8 alkyl), C(═S)N(C.sub.1-C.sub.8 alkyl)(C.sub.1-C.sub.8 alkyl), SO.sub.2N(C.sub.1-C.sub.8 alkyl)(C.sub.1-C.sub.8 alkyl), OSO.sub.2(C.sub.1-C.sub.8 alkyl), OSO.sub.2N(C.sub.1-C.sub.8 alkyl)(C.sub.1-C.sub.8 alkyl), N(C.sub.1-C.sub.8 alkyl)SO.sub.2(C.sub.1-C.sub.8 alkyl), or C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 haloalkyl, C.sub.2-C.sub.8 alkenyl, C.sub.2-C.sub.8 alkynyl, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10 halocycloalkyl, C.sub.4-C.sub.10 alkylcycloalkyl, C.sub.4-C.sub.10 cycloalkylalkyl, C.sub.6-C.sub.14 cycloalkylcycloalkyl, C.sub.5-C.sub.10 alkylcycloalkylalkyl, C.sub.3-C.sub.8 cycloalkenyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 haloalkoxy, C.sub.3-C.sub.8 cycloalkoxy, C.sub.3-C.sub.8 halocycloalkoxy, C.sub.4-C.sub.10 cycloalkylalkoxy, C.sub.2-C.sub.8 alkenyloxy, C.sub.2-C.sub.8 alkynyloxy, C.sub.1-C.sub.8 alkylthio, C.sub.1-C.sub.8 alkylsulfinyl, C.sub.1-C.sub.8 alkylsulfonyl, C.sub.3-C.sub.8 cycloalkylthio, C.sub.3-C.sub.8 cycloalkylsulfinyl, C.sub.3-C.sub.8 cycloalkylsulfonyl, C.sub.4-C.sub.10 cycloalkylalkylthio, C.sub.4-C.sub.10 cycloalkylalkylsulfinyl, C.sub.4-C.sub.10 cycloalkylalkylsulfonyl, C.sub.2-C.sub.8 alkenylthio, C.sub.2-C.sub.8 alkenylsulfinyl, C.sub.2-C.sub.8 alkenylsulfonyl, C.sub.2-C.sub.8 alkynylthio, C.sub.2-C.sub.8 alkynylsulfinyl, C.sub.2-C.sub.8 alkynylsulfonyl, or phenyl; or two of R.sup.1, R.sup.2, and R.sup.3 on adjacent ring atoms may be taken together to form a 5- to 7-membered carbocyclic or heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2 O, up to 2 S, and up to 3 N, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S) and such ring is optionally substituted with up to 3 substituents independently selected from the group consisting of C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.2-C.sub.4 haloalkynyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.7 halocycloalkyl, C.sub.4-C.sub.8 alkylcycloalkyl, C.sub.4-C.sub.8 haloalkylcycloalkyl, C.sub.4-C.sub.8 cycloalkylalkyl, C.sub.4-C.sub.8 halocycloalkylalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 haloalkoxy, C.sub.2-C.sub.8 alkoxycarbonyl, C.sub.2-C.sub.6 haloalkoxycarbonyl, C.sub.2-C.sub.6 alkylcarbonyl and C.sub.2-C.sub.6 haloalkylcarbonyl; and M is an inorganic cation or organic cation; comprising: (a) contacting a compound of Formula A ##STR00039## with a solvent selected from o-dichlorobenzene (ODCB), chloroalkanes, and chloroarenes, and a first acid selected from sulfonic acids, sulfuric acid (H.sub.2SO.sub.4), and oleum to form a compound of Formula B: ##STR00040## and (b) contacting the compound of Formula B with (i) a nitrite salt MNO.sub.2 or nitrite ester and (ii) a second acid selected from at least one inorganic acid, at least one organic acid, or mixtures thereof to form a compound of Formula C: ##STR00041##

2. The method of claim 1, wherein each R.sup.1, R.sup.2, and R.sup.3 is independently H, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, or phenyl.

3. The method of claim 1, wherein R.sup.2 is CH.sub.3, CH.sub.2CH.sub.3, CF.sub.3, OCH.sub.3, OCF.sub.3, or OCH.sub.2CH.sub.3.

4. The method of claim 1, wherein the second acid comprises an inorganic acid selected from hydrochloric acid (HCl), hydrobromic acid (HBr), phosphoric acid (H.sub.3PO.sub.4), sulfuric acid (H.sub.2SO.sub.4), and boric acid (H.sub.3BO.sub.3).

5. The method of claim 1, wherein the second acid comprises an organic acid selected from formic acid, acetic acid, propionic acid, citric acid, malic acid, and sulfonic acids.

Description

DETAILED DESCRIPTION

(1) As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains”, “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.

(2) The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such phrase would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

(3) Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of” or “consisting of.”

(4) Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

(5) Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

(6) The term “ambient temperature” or “room temperature” as used in this disclosure refers to a temperature between about 18° C. and about 28° C.

(7) In the above recitations, the term “alkyl”, includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl isomers. As used herein, haloalkanes are alkanes partially or fully substituted with halogen atoms (fluorine, chlorine, bromine or iodine). Examples of haloalkanes include CH.sub.2Cl.sub.2, ClCH.sub.2CH.sub.2Cl, ClCH.sub.2CH.sub.2CH.sub.2CH.sub.3, and CCl.sub.3CH.sub.3. Halogenated benzenes are benzenes partially or fully substituted with halogen atoms (fluorine, chlorine, bromine or iodine). Examples of halogenated benzenes include chlorobenzene, 1,2-dichlorobenzene and bromobenzene. C.sub.7-C.sub.10 aromatic hydrocarbons are compounds containing one benzene ring which is substituted with alkyl groups. Examples of C.sub.7-C.sub.10 aromatic hydrocarbons include toluene, xylenes, ethyl benzene and cumene (isopropylbenzene). C.sub.5-C.sub.10 aliphatic hydrocarbons are straight-chain or branched hydrocarbons. Examples of C.sub.5-C.sub.10 aliphatic hydrocarbons include n-hexane, mixed hexanes, n-heptane and mixed heptanes. C.sub.5-C.sub.10 cycloaliphatic hydrocarbons are cyclic hydrocarbons that can be substituted with straight-chain or branched alkyl groups. Examples of C.sub.5-C.sub.10 cycloaliphatic hydrocarbons include cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane.

(8) The first aspect of the invention provides a method of preparing a compound of Formula 1:

(9) ##STR00032##

(10) In some embodiments as shown in Scheme 1, a compound of Formula 2 can be converted to the arylsulfonic acid compound of Formula 3 via reaction with sulfuric acid. Next the compound of Formula 3 can be diazotized to form a compound of Formula 4, which can then be converted to the chloroarylsulfonate sodium salt compound of Formula 5 via a Sandmeyer reaction, wherein M is an inorganic cation or organic cation. Next the compound of Formula 5 can be converted to the chloroarylsulfonyl chloride compound of Formula 6 with thionyl chloride and catalytic dimethylformamide (DMF). Subsequent addition of aqueous ammonia can result in a compound of Formula 1.

(11) ##STR00033##

(12) In some embodiments, M is an inorganic cation selected from sodium, potassium, ammonium, lithium, and mixtures thereof. In some embodiments, M is sodium. In some embodiments, M is an organic cation selected from trimethylammonium, triethylammonium, tri-n-propylammonium, triisopropylammonium, and tributylammonium.

(13) The reactions shown in Scheme 1 can be accomplished in a solvent is selected from water, C.sub.7-C.sub.10 aromatic hydrocarbons, haloalkanes, halogenated benzenes, C.sub.5-C.sub.10 aliphatic hydrocarbons, C.sub.5-C.sub.10 cycloaliphatic hydrocarbons, acetonitrile, or combinations thereof. In some embodiments, water, toluene, dichloromethane, 1,2-dichloroethane, I-chlorobutane, acetonitrile, or combinations thereof can be used. Other suitable solvent include xylenes, ethylbenzene, and cumene.

(14) The reactions shown in Scheme 1 can be conducted under a broad range of temperatures, i.e., temperatures in the range from 20° C. to 150° C.; or from 50° C. to 200° C. Temperatures in the range from 50° C. to 180° C.; or from 60° C. to 100° C. are particularly useful. Temperatures in the range of 60° C. to 80° C. are especially useful.

(15) The process shown in Scheme 1 is more efficient and reduces the cost of production for the compound of Formula 1 as compared to previously disclosed processes. Other advantages include safer process by avoiding pyrophoric reagents, better volume efficiency, better reaction kinetics, and/or reduced foaming problem.

(16) The second aspect of the invention provides a method of preparing a compound of Formula 7:

(17) ##STR00034##

(18) In some embodiments as shown in Scheme 2, a compound of Formula 8 can be converted to the acid chloride compound of Formula 7 via an amine salt compound of Formula 9. A Reagent A selected from trimethylamine, triethylamine, pyridine, alkylpyridines, and 3-picoline (or 3-methylpyridine) can be used in this conversion process.

(19) ##STR00035##

(20) The third aspect of the invention provides a method of preparing a compound of Formula 10:

(21) ##STR00036##

(22) In some embodiments as shown in Scheme 3, a compound of Formula 1 and a compound of Formula 7 are used for a coupling reaction in the presence of a Reagent B selected from trimethylamine, pyridine, and 3-picoline (or 3-methylpyridine) to form a compound of Formula 11. Next the compound of Formula 11 is neutralized with an acid to form the compound of Formula 10.

(23) Subsequent addition of water and seed crystals can induce crystallization of desired polymorph form as previously disclosed.

(24) Suitable acid can be an inorganic acid selected from hydrochloric acid (HCl), hydrobromic acid (HBr), phosphoric acid (H.sub.3PO.sub.4), sulfuric acid (H.sub.2SO.sub.4), and boric acid (H.sub.3BO.sub.3). In some embodiments, the acid comprises hydrochloric acid (HCl). Other suitable acid can be an organic acid selected from formic acid, acetic acid, propionic acid, citric acid, malic acid, and sulfonic acids. In some embodiments, the acid comprises sulfonic acids. Examples of sulfonic acids including para-toluenesulfonic acid, methanesulfonic acid, and toluenesulfonic acid as a mixture of isomers. In some embodiments, the coupling step shown in Scheme 3 does not use a base. In some embodiments, the coupling step shown in Scheme 3 does not use any solvent comprising ethers, esters, and/or halogenated hydrocarbons.

(25) ##STR00037##

(26) The coupling step shown in Scheme 3 can be accomplished in a solvent selected from water, C.sub.7-C.sub.10 aromatic hydrocarbons. C.sub.5-C.sub.10 aliphatic hydrocarbons, C.sub.5-C.sub.10 cycloaliphatic hydrocarbons, acetonitrile, or combinations thereof. In some embodiments, water, toluene, acetonitrile, or combinations thereof can be used. Other suitable solvent include xylenes, ethylbenzene, and cumene.

(27) The coupling step shown in Scheme 3 can be run under a broad range of temperatures, i.e., temperatures in the range from 20° C. to 150° C.; or from 40° C. to 100 CC. Temperatures in the range from 50° C. to 100° C. are particularly useful. Temperatures in the range from 50° C. to 80° C.; or from 60° C. to 75° C. are especially useful.

(28) The molar ratio of the compound of Formula 1 to the compound of Formula 7 can be in the range of 2:1 to 1:2; 1.5:1.0 to 1.0:1.5; 1.2:1.0 to 1.0:1.2; 1.1:1.0 to 1.0:1.1; and/or 1:1.

(29) Again, the processes shown in Schemes 2 and/or 3 reduce the cost of production and avoid the use of a pyrophoric reagent as compared to previously disclosed processes. The processes shown in Scheme 2 and/or 3 also have other advantages including safer process by avoiding pyrophoric reagents, better volume efficiency, better reaction kinectics, reduced foaming problem, and/or a more efficient control of the Formula 10 polymorph that crystallizes as compared to previously disclosed processes (for example selecting different polymorph).

Preparation Example 1

Synthesis of Compound of Formula 3

(30) To a 1 L round bottom flask equipped with an overhead mechanical stirrer, a 10 cm glass spring packing, a modified Dean-Stark trap, a thermometer, a condenser and a nitrogen inlet and outlet is charged p-anisidine (67 g; 0.539 mol) and o-dichlorobenzene (ODCB, 359.4 mL, 5.26 vol). 70% Sulfuric acid (98 wt %, 50.1 g, 27.2 ml, 0.501 mol) is added into 20 g of water and then added dropwise to the reactor while maintaining the internal temperature at <60° C. The reaction mixture was agitated for 30 min. The resulting gray white slurry was heated to 170° C. and reflux-distilled to remove water at atmospheric pressure. The reaction mass was agitated at 170-176° C. until the content of p-anisidine was <7%. The reaction mass is filtered and washed with o-dichlorobenzene. The compound of Formula 3 wet product (125.1 g, ˜70 wt %, 0.431 mol) is obtained as a light gray solid with purity >97.5% by HPLC (High Performance Liquid Chromatography).

Preparation Example 2

Synthesis of Compound of Formula 4 and 5

(31) To a 1 L round bottom flask equipped with an overhead stirrer, a thermocouple, and a nitrogen inlet/outlet is charged concentrated hydrochloric acid (30% wt %, 314.2 g, 261.8 mL, 2,585 mol) and water (76.7 mL, 0.88 vol). The compound of Formula 3 wet product (125.1 g, ˜70 wt %, 0.431 mol) is added and the resulting slurry is cooled to <10° C. A solution of sodium nitrite (31.2 g, 98%, 0.444 mol) dissolved in water (87.6 mL) is added slowly and the reaction is stirred for 1 h. Sulfamic acid (2.1 g, 98%, 0.222 mol) is then dissolved in water (43.6 mL) and the solution is added to the reaction mass to form compound of Formula 4.

(32) Water (87.6 ml) is then added to a second 1 L round bottom flask followed by copper powder (˜150 mesh, 3.4 g, 0.054 mol) and the slurry stirred at room temperature. The reaction mass is transferred slowly to the copper slurry and agitated for about two hours.

(33) The reaction mixture is cooled to <25° C. and then 50% NaOH aqueous solution (98% NaOH, 35.1 g, 2.0 mol, dissolved in 33.7 g of water) is added dropwise until pH reaches 2.5-3.5. The resulting dark yellow slurry is agitated for another two hours then filtered. After suction-dried the resulting compound of Formula 5 product (108.0 g, 0.353 mol) is obtained with purity >98% by HPLC.

Preparation Example 3

Synthesis of Compound of Formula 6

(34) To a 1 L round bottom flask equipped with an overhead mechanical stirrer, a Dean-Stark trap, a thermometer, and a condenser is charged the compound of Formula 5 from the last example followed by toluene (432.1 mL). The resulting slurry is heated to remove water content. The slurry is cooled to 60-65° C. and N, N-dimethylformamide (4.1 mL, 0.053 mol) is added to the reactor followed by thionyl chloride (64.2 mL, 0.883 mol). After 2 h the reaction mass is distilled to ˜½ the volume and toluene (259.3 mL) is added to the slurry followed by further distillation. The resulting slurry is filtered through a Celite pad (8.6 g) and the pad is washed with toluene (86.4 mL) where the filtrate gives compound for Formula 6.

Preparation Example 4

Synthesis of Compound of Formula 1

(35) To a 1 L round bottomed flask is charged aqueous ammonia (28 wt %, 158.5 mL, 2.346 mol) and acetonitrile (176.7 ml) under a nitrogen atmosphere. The compound of Formula 6 from the last example is added to the solution and agitated for about two and half hours, resulting in two separate layers. The layers are separated and the lower aqueous layer is mixed with toluene (1.0 vol) and acetonitrile (1.0 vol) for further agitation, again resulting two separate layers. The combined organic layers are treated with activated carbon (3.0 wt %) and then filtered through a Büchner funnel and concentrated to afford compound of Formula 1, which is dried in a vacuum oven to give a light brown solid with purity >99% by HPLC.

Preparation Example 5

Synthesis of Compound of Formula 7

(36) To a 100-mL 3-neck flask equipped with a condenser, addition funnel, thermocouple, heating mantle, and magnetic stirrer is charged a compound of Formula 8 (10.01 g, 37.5 mmol), acetonitrile (27 mL), and 3-picoline (2.824 g, 30.0 mmol). The mixture is heated to ˜65° C., and then a solution of thionyl chloride (5.40 g, 44.9 mmol) in acetonitrile (3 mL) is added dropwise over ˜20 minutes while maintaining the temperature between 63-71° C. After the addition is complete, the reaction mixture is heated at 70° C. for about two hours and then allowed to cool to ambient temperature to give compound of Formula 7 as a solution in acetonitrile.

Preparation Example 6

Synthesis of Compound of Formula 10—

Coupling Reaction Using Compounds of Formula 1 and 7

(37) To a separate 125 mL 4-neck jacketed round bottom flask equipped with a magnetic stirrer, condenser, thermocouple and circulating bath, is charged compound of Formula 1 (10.05 g, 44.9 mmol), 3-picoline (8.462 g, 90.0 mmol), and acetonitrile (10 mL). The mixture is heated to ˜58° C., and then the compound of Formula 7 is added dropwise via a peristaltic pump over ˜1.5 hours while maintaining the reaction temperature between 55-60° C. The reaction is heated at ˜60° C. for ˜1 hr and then concentrated hydrochloric acid (˜37% by weight, 3.895 g, 39.4 mmol) and water (0.5 mL) are then added to give to give an aqueous acetonitrile solution of Compound 10. The solution is heated to ˜70° C. and then a slurry of Formula 10 seed crystals (0.195 g) in water (28 g) is added over ˜2 hr. After adding more water (10 g), the resulting slurry is refluxed for ˜1.5 hrs, cooled to ambient temperature, and then filtered. The wet cake is washed with aqueous acetonitrile and dried to give a compound of Formula 10 as an off-white to light brown solid in about 90% yield and ˜98% purity.