Processes for preparing dihydropyrimidine derivatives and intermediates thereof

1. A process for preparing a dihydropyrimidine compound having Formula (I), or a tautomer thereof having Formula (Ia),

wherein each R 1 and R 2 is independently F, Cl, or Br;

R 3 is C 1-4 alkyl;

Z is —O—, —S—, —S(═O) t , or —N(R 4 )—;

Y is —O—, —S—, —S(═O) t , —(CH 2 ) q —, or —N(R 5 )—;

each t and q is independently 0, 1, or 2;

each of R 4 and R 5 is independently H or C 1-4 alkyl;

each R 6 is independently H, deuterium, halo, C 1-4 alkyl, C 1-4 haloalkyl, amino, C 1-4 alkylamino, C 1-4 alkoxy, nitro, triazolyl, tetrazyl, —(CR 7 R 7a ) m —OH, —S(═O) q OR 8a , —(CR 7 R 7a ) m —S(═O) q N(R 8a ) 2 , —(CR 7 R 7a ) t —N(R 8a ) 2 , —(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)O—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) m —OC(═O)—R 8 , or —(CR 7 R 7a ) m —C(═O)—N(R 8 R 8a );

each R 7a and R 7 is independently H, halo, C 1-4 alkyl, C 1-4 haloalkyl, —(CH 2 ) m —OH, or —(CH 2 ) m —C(═O)O—R 8 ; or R 7a and R 7 , together with the carbon atom to which they are attached, form a C 3-6 cycloalkyl group, C 2-9 heterocyclyl group, or —(C═O)—;

each R 8 and R 8a is independently H, C 1-4 alkyl, amino-C 1-4 -alkyl, C 1-4 alkoxy, C 1-6 alkyl-S(═O) q —, C 6-10 aryl, C 1-9 heteroaryl, C 3-6 cycloalkyl, C 2-9 heterocyclyl, C 6-10 aryl-C 1-6 -alkyl, C 1-9 heteroaryl-C 1-6 -alkyl, C 3-6 cycloalkyl-C 1-4 -alkyl, C 2-9 heterocyclyl-C 1-6 -alkyl, C 2-9 heterocyclyl-S(═O) q —, C 1-9 heteroaryl-S(═O) q —, C 3-6 cycloalkyl-S(═O) q —, C 6-10 aryl-S(═O) q —, —(CH 2 ) m —OH, —(CH 2 ) m —C(═O)O—(CH 2 ) m —H, or —(CH 2 ) m —OC(═O)—(CH 2 ) m —H;

each R 9 is independently H, halo, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkylthio, C 3-6 cycloalkyl, —(CR 7 R 7a ) m —C(═O)—N(R 8 R 8a ), or —(CR 7a ) m —C(═O)O—R 8 ;

R 10 is H or deuterium;

n is 0, 1, 2, 3, 4, or 5;

each m is independently 0, 1, 2, 3, or 4;

f is 1, 2, 3, or 4; and

j is 0, 1, or 2;

wherein the process comprises the steps of:

step (A): reacting an amidine compound of Formula (II), or a salt thereof

with an aldehyde compound of Formula (III)

and a compound of Formula (IVa)

in a first organic solvent to obtain a compound of Formula (Va),

wherein R 3b is methoxy or ethoxy; and

R 3a is H or C 1-3 alkyl;

step (B): halogenating the compound of Formula (Va) in a third organic solvent to form a halide; and then reacting the halide with a compound of Formula (VI), or a salt thereof to obtain a compound of Formula (VIIa),

and

step (C): forming the compound of Formula (I) or Formula (Ia) from the compound of Formula (VIIa) by means of a transesterification.

2. The process of claim 1 , wherein the dihydropyrimidine compound has Formula (I-1), or a tautomer thereof having Formula (Ia-1),

wherein, each R 6 is independently H, halo, C 1-4 alkyl, C 1-4 haloalkyl, amino, C 1-4 alkylamino, C 1-4 alkoxy, nitro, triazolyl, tetrazyl, —(CR 7 R 7a ) m —OH, —S(═O) q OR 8a , —(CR 7 R 7a ) m —S(═O) q N(R 8a ) 2 , —(CR 7 R 7a ) t —N(R 8a ) 2 , —(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)O—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) m —OC(═O)—R 8 , or —(CR 7 R 7a ) m —C(═O)—N(R 8 R 8a ); and

each R 7a and R 7 is independently H, C 1-4 alkyl, C 1-4 haloalkyl, —(CH 2 ) m —OH, or —(CH 2 ) m —C(═O)O—R 8 .

3. The process of claim 2 , wherein the dihydropyrimidine compound has Formula (I-2), or a tautomer thereof having Formula (Ia-2),

wherein R 1 is F or Cl; and R 2 is Cl or Br.

4. The process of claim 1 , wherein

R 3 is methyl, ethyl, propyl, isopropyl, tert-butyl, or butyl;

Z is —O—, —S—, or —N(CH 3 )—;

Y is —O—, —S—, —S(═O) 2 —, or —(CH 2 ) q —;

each R 6 is independently H, halo, C 1-4 alkyl, C 1-4 haloalkyl, amino, C 1-4 alkylamino, C 1-4 alkoxy, nitro, triazolyl, tetrazyl, —(CR 7 R 7a ) m —OH, —(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) t —N(R 8a ) 2 , —S(═O) q OR 8a , —(CR 7 R 7a ) m —S(═O) q N(R 8a ) 2 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)O—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) m —OC(═O)—R 8 , or —(CR 7 R 7a ) m —C(═O)N(R 8 R 8a );

each R 7a and R 7 is independently H, methyl, ethyl, trifluoromethyl, —(CH 2 ) m —OH, or —(CH 2 ) m —C(═O)O—R 8 ;

each R 8 and R 8a is independently H, methyl, ethyl, propyl, isopropyl, aminomethyl, methoxy, C 1-4 alkyl-S(═O) 2 —, phenyl, pyridyl, thiazolyl, furanyl, imidazolyl, isoxazolyl, oxazolyl, pyrrolyl, pyrimidinyl, pyridazinyl, diazolyl, triazolyl, tetrazolyl, thienyl, pyrazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyrazinyl, pyranyl, triazinyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl-S(═O) 2 —, cyclobutyl-S(═O) 2 —, cyclopentyl-S(═O) 2 —, cyclohexyl-S(═O) 2 —, naphthyl-S(═O) 2 —, phenyl-S(═O) 2 —, —(CH 2 ) m —OH, —(CH 2 ) m —C(═O)O—(CH 2 ) m —H, or —(CH 2 ) m —OC(═O)—(CH 2 ) m —H;

R 3b is methoxy or ethoxy; and

R 3a is H, methyl, ethyl, isopropyl, or propyl.

5. The process of claim 1 , wherein the reaction in step (A) is performed at a temperature from 25° C. to 154° C. or from 60° C. to 100° C.

6. The process of claim 1 , wherein the step (A) further comprises a step of cooling the resulting compound of Formula (Va) of step (A) to obtain a solid compound of Formula (Va) at a cooling temperature from −40° C. to 40° C. or from 25° C. to 40° C.

7. The process of claim 6 , wherein the cooling is performed for a period of from 0 hour to 24 hours, or from 1 minute to 24 hours, or from 1 hour to 8 hours.

8. The process of claim 1 , wherein the first organic solvent is applied in an amount of 0 equivalent to 80 equivalents, or 1 equivalent to 20 equivalents per 1 equivalent by weight of the amidine compound of Formula (II), or a salt thereof.

9. The process of claim 1 , wherein step (A) further comprises a step of purifying the compound of Formula (Va) in a second organic solvent, wherein the compound of Formula (Va) is purified by at least one of the following methods:

(1) trituration, wherein the trituration is carried out at a temperature from −20° C. to 50° C. or from 0° C. to 40° C.;

(2) recrystallization, wherein the recrystallization comprises a crystallization process at a temperature from −30° C. to 40° C. or from 0° C. to 40° C., and wherein the recrystallization comprises a crystallization process of from 1 hour to 20 hours or from 1 hour to 10 hours; or

(3) washing, wherein the washing is performed at a temperature from 0° C. to 30° C.

10. The process of claim 9 , wherein the second organic solvent is applied in an amount of 2 equivalent to 20 equivalents per 1 equivalent by weight of the amidine compound of Formula (II), or a salt thereof.

11. The process of claim 9 , wherein each of the first organic solvent and the second organic solvent is independently a C 1-4 alcohol, a C 1-4 alcohol-water mixture, acetone, diethyl ether, isopropyl ether, petroleum ether, tetrahydrofuran, acetonitrile, cyclopentane, cyclohexane, n-hexane, a C 1-4 haloalkane solvent, ethyl acetate, trifluoroethanol, 2-methoxyethanol, 1,2-dimethoxyethane, 2-methoxyethyl ether, N,N-dimethyl formamide, N-methylpyrolidone, or a combination thereof, or wherein each of the first organic solvent and the second organic solvent is independently methanol, ethanol, n-propanol, i-propanol, n-butanol, tert-butanol, an ethanol-water mixture at a volume ratio of from 10:90 to 90:10, acetone, tetrahydrofuran, N-methylpyrolidone, trifluoroethanol, 2-methoxyethanol, 1,2-dimethoxyethane, 2-methoxyethyl ether, ethyl acetate, glycol, N,N-dimethyl formamide, or a combination thereof.

12. The process of claim 1 , wherein the third organic solvent is one or more C 1-4 alcohols, one or more C 1-4 haloalkanes, acetonitrile, isopropyl ether, petroleum ether, toluene, xylene, tetrahydrofuran, ethyl acetate, acetone, or a combination thereof, or wherein the third organic solvent is dichloromethane, chloroform, tetrachloromethane, acetonitrile, isopropyl ether, petroleum ether, tetrahydrofuran, methanol, ethanol, propanol, i-propanol, n-butanol, tert-butanol, ethyl acetate, acetone, or a combination thereof.

13. The process of claim 1 , wherein the halogenating reaction in step (B) is carried out in the presence of a halogenating agent, and wherein the halogenating agent is N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, or 1,3-dichloro-5,5-dimethylhydantoin, or a combination thereof.

14. The process of claim 1 , wherein the transesterification in step (C) is performed in the presence of a base, and wherein the base is formed by reacting lithium, sodium, or potassium or a combination thereof with a C 1-4 alcohol.

15. The process of claim 14 , wherein the C 1-4 alcohol is methanol, ethanol, propanol, i-propanol, n-butanol, i-butanol, or tert-butanol, and wherein the lithium, sodium or potassium or a combination thereof is applied in an amount of 2 equivalents to 6 equivalents per 1 equivalent by mole of the compound of Formula (VIIa).

16. The process of claim 1 , wherein the compound of Formula (IVa) in step (A) is prepared by a process comprising reacting a compound of Formula (VIIIa) with a compound of Formula (IX),

17. A compound having Formula (Va), or a tautomer thereof having Formula (Va1), or a salt thereof, or a combination thereof,

wherein each R 1 and R 2 is independently F, Cl, or Br;

R 3b is methoxy or ethoxy;

R 3a is H or C 1-3 alkyl;

each R 9 is independently H, halo, C 1-4 alkyl, C 1-4 alkylthio, C 1-4 haloalkyl, C 3-6 cycloalkyl, —(CR 7 R 7a ) m —C(═O)—N(R 8 R 8a ), or —(CR 7 R 7a ) m —C(═O)O—R 8 ;

each R 7a and R 7 is independently H, halo, C 1-4 alkyl, C 1-4 haloalkyl, —(CH 2 ) m —OH, or —(CH 2 ) m —C(═O)O—R 8 ; or R 7a and R 7 , together with the carbon atom to which they are attached, form a C 3-6 cycloalkyl group, C 2-9 heterocyclyl group, or —(C═O)—;

each R 8 and R 8a is independently H, C 1-4 alkyl, amino-C 1-4 -alkyl, C 1-4 alkoxy, C 1-6 alkyl-S(═O) q —, C 6-10 aryl, C 1-9 heteroaryl, C 3-6 cycloalkyl, C 2-9 heterocyclyl, C 6-10 aryl-C 1-6 -alkyl, C 1-9 heteroaryl-C 1-6 -alkyl, C 3-6 cycloalkyl-C 1-4 -alkyl, C 2-9 heterocyclyl-C 1-6 -alkyl, C 2-9 heterocyclyl-S(═O) q —, C 1-9 heteroaryl-S(═O) q —, C 3-6 cycloalkyl-S(═O) q —, C 6-10 aryl-S(═O) q —, —(CH 2 ) m —OH, —(CH 2 ) m —C(═O)O—(CH 2 ) m —H, or —(CH 2 ) m —OC(═O)—(CH 2 ) m —H;

each m is independently 0, 1, 2, 3, or 4;

R 10 is H or deuterium;

f is 1, 2, 3, or 4;

j is 0, 1, or 2;

Z is —O—, —S—, —S(═O) t , or —N(R 4 )—;

t is 0, 1, or 2; and

R 4 is H or C 1-4 alkyl.

18. The compound of claim 17 having Formula (Va-1), or a tautomer thereof having Formula (Va1-1), or a salt thereof, or a combination thereof,

19. The compound of claim 17 having Formula (Va-2), or a tautomer thereof having Formula (Va1-2), or a salt thereof, or a combination thereof,

wherein R 1 is F or Cl; and R 2 is Cl or Br;

Z is —O—, —S—, or —N(CH 3 )—;

R 3b is methoxy or ethoxy; and

R 3a is H, methyl, ethyl, isopropyl, or propyl.

20. A process for preparing a dihydropyrimidine compound having Formula (I), or a tautomer thereof having Formula (Ia),

wherein each R 1 and R 2 is independently F, Cl, or Br;

R 3 is C 1-4 alkyl;

Z is —O—, —S—, —S(═O) t , or —N(R 4 )—;

Y is —O—, —S—, —S(═O) t , —(CH 2 )q-, or —N(R 5 )—;

each t and q is independently 0, 1, or 2;

each of R 4 and R 5 is independently H or C 1-4 alkyl;

each R 6 is independently H, deuterium, halo, C 1-4 alkyl, C 1-4 haloalkyl, amino, C 1-4 alkylamino, C 1-4 alkoxy, nitro, triazolyl, tetrazyl, —(CR 7 R 7a ) m —OH, —(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) t —N(R 8a ) 2 , —S(═O) q OR 8a , —(CR 7 R 7a ) m —S(═O) q N(R 8a ) 2 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)O—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) m —OC(═O)—R 8 , or —(CR 7 R 7a ) m —C(═O)N(R 8 R 8a );

each R 7a and R 7 is independently H, halo, C 1-4 alkyl, C 1-4 haloalkyl, or —(CH 2 ) m —C(═O)O—R 8 ; or R 7a and R 7 , together with the carbon atom to which they are attached, form a C 3-6 cycloalkyl group, C 2-9 heterocyclyl group, or —(C═O)—;

each R 8 and R 8a is independently H, C 1-4 alkyl, amino-C 1-4 -alkyl, C 1-4 alkoxy, C 1-6 alkyl-S(═O) q —, C 6-10 aryl, C 1-9 heteroaryl, C 3-6 cycloalkyl, C 2-9 heterocyclyl, C 6-10 aryl-C 1-6 -alkyl, C 1-9 heteroaryl-C 1-6 -alkyl, C 3-6 cycloalkyl-C 1-4 -alkyl, C 2-9 heterocyclyl-C 1-6 -alkyl, C 2-9 heterocyclyl-S(═O) q —, C 1-9 heteroaryl-S(═O) q —, C 3-6 cycloalkyl-S(═O) q —, C 6-10 aryl-S(═O) q —, —(CH 2 ) m —OH, —(CH 2 ) m —C(═O)O—(CH 2 ) m —H, or —(CH 2 ) m —OC(═O)—(CH 2 ) m —H;

each R 9 is independently H, halo, C 1-4 alkyl, C 1-4 alkylthio, C 1-4 haloalkyl, C 3-6 cycloalkyl, —(CR 7 R 7a ) m —C(═O)—N(R 8 R 8a ), or —(CR 7 R 7a ) m —C(═O)O—R 8 ;

R 10 is H or deuterium;

n is 0, 1, 2, 3, 4, or 5;

each m is independently 0, 1, 2, 3, or 4;

f is 1, 2, 3, or 4; and

j is 0, 1, or 2;

wherein the process comprises the steps of:

step (1): reacting an amidine compound of Formula (II), or a salt thereof

with an aldehyde compound of Formula (III)

and a compound of Formula (IVa)

to obtain a compound (Va),

step (2): forming a compound of Formula (X) from a compound of Formula (Va) by means of a transesterification,

wherein R 3b is methoxy or ethoxy; and

R 3a is H or C 1-3 alkyl; and

step (3): halogenating the compound of Formula (X) in a fourth organic solvent to form a halide; and then reacting the halide with a compound of Formula (VI), or a salt thereof to obtain a compound of Formula (I) or Formula (Ia),

21. The process of claim 20 , wherein the dihydropyrimidine compound has Formula (I-1), or a tautomer thereof having Formula (Ia-1),

wherein, each R 6 is independently H, halo, C 1-4 alkyl, C 1-4 haloalkyl, amino, C 1-4 alkylamino, C 1-4 alkoxy, nitro, triazolyl, tetrazyl, —(CR 7 R 7a ) m —OH, —(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) t —N(R 8a ) 2 , —S(═O) q OR 8a , —(CR 7 R 7a ) m —S(═O) q N(R 8a ) 2 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)O—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) m —OC(═O)—R 8 , or —(CR 7 R 7a ) m —C(═O)N(R 8 R 8a ); and

each R 7a and R 7 is independently H, C 1-4 alkyl, C 1-4 haloalkyl, —(CH 2 ) m —OH, or —(CH 2 ) m —C(═O)O—R 8 .

22. The process of claim 21 , wherein the dihydropyrimidine compound has Formula (I-2), or a tautomer thereof having Formula (Ia-2),

wherein R 1 is F or Cl; and R 2 is Cl or Br.

23. The process of claim 20 , wherein

R 3 is methyl, ethyl, propyl, isopropyl, tert-butyl, or butyl;

Z is —O—, —S—, or —N(CH 3 )—;

Y is —O—, —S—, —S(═O) 2 —, or —(CH 2 ) q —;

each R 6 is independently H, halo, C 1-4 alkyl, C 1-4 haloalkyl, amino, C 1-4 alkylamino, C 1-4 alkoxy, nitro, triazolyl, tetrazyl, —(CR 7 R 7a ) m —OH, —S(═O) q OR 8a , —(CR 7 R 7a ) m —S(═O) q N(R 8a ) 2 , —(CR 7 R 7a ) t —N(R 8a ) 2 , —(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)O—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —OC(═O)—R 8 , —(CR 7 R 7a ) m —C(═O)O—(CR 7 R 7a ) m —C(═O)O—R 8 , —(CR 7 R 7a ) m —OC(═O)—R 8 , or —(CR 7 R 7a ) m —C(═O)—N(R 8 R 8a );

each R 7a and R 7 is independently H, methyl, ethyl, trifluoromethyl, or —(CH 2 ) m —C(═O)O—R 8 ;

each R 8 and R 8a is independently H, methyl, ethyl, propyl, isopropyl, aminomethyl, methoxy, C 1-4 alkyl-S(═O) 2 —, phenyl, pyridyl, thiazolyl, furanyl, imidazolyl, isoxazolyl, oxazolyl, pyrrolyl, pyrimidinyl, pyridazinyl, diazolyl, triazolyl, tetrazolyl, thienyl, pyrazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyrazinyl, pyranyl, triazinyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl-S(═O) 2 —, cyclobutyl-S(═O) 2 —, cyclopentyl-S(═O) 2 —, cyclohexyl-S(═O) 2 —, naphthyl-S(═O) 2 —, phenyl-S(═O) 2 —, —(CH 2 ) m —OH, —(CH 2 ) m —C(═O)O—(CH 2 ) m —H, or —(CH 2 ) m —OC(═O)—(CH 2 ) m —H;

R 3b is methoxy or ethoxy; and

R 3a is H, methyl, ethyl, isopropyl, or propyl.

24. The process of claim 20 , wherein the transesterification in step (2) is performed in the present of a base, wherein the base is formed by reacting lithium, sodium, or potassium or a combination thereof with a C 1-4 alcohol, wherein the C 1-4 alcohol is methanol, ethanol, propanol, i-propanol, n-butanol, i-butanol, or tert-butanol, and wherein the lithium, sodium, potassium or a combination thereof is applied in an amount of 2 equivalents to 8 equivalents per 1 equivalent by mole of the compound of Formula (Va).

25. The process of claim 20 , wherein the fourth organic solvent is one or more C 1-4 alcohols, one or more C 1-4 haloalkanes, ethyl acetate, acetonitrile, isopropyl ether, petroleum ether, toluene, xylene, tetrahydrofuran, acetone, or a combination thereof, or the forth organic solvent is methanol, ethanol, propanol, i-propanol, n-butanol, tert-butanol, dichloromethane, chloroform, tetrachloromethane, ethyl acetate, acetonitrile, isopropyl ether, petroleum ether, tetrahydrofuran, acetone, or a combination thereof.

26. The process of claim 20 , wherein the halogenating reaction in step (3) is carried out in the presence of a halogenating agent, and wherein the halogenating agent is N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin, or a combination thereof.

27. The process of claim 10 , wherein each of the first organic solvent and the second organic solvent is independently a C 1-4 alcohol, a C 1-4 alcohol-water mixture, acetone, diethyl ether, isopropyl ether, petroleum ether, tetrahydrofuran, acetonitrile, cyclopentane, cyclohexane, n-hexane, a C 1-4 haloalkane solvent, ethyl acetate, trifluoroethanol, 2-methoxyethanol, 1,2-dimethoxyethane, 2-methoxyethyl ether, N,N-dimethyl formamide, N-methylpyrolidone, or a combination thereof, or wherein each of the first organic solvent and the second organic solvent is independently methanol, ethanol, n-propanol, i-propanol, n-butanol, tert-butanol, an ethanol-water mixture at a volume ratio of from 10:90 to 90:10, acetone, tetrahydrofuran, N-methylpyrolidone, trifluoroethanol, 2-methoxyethanol, 1,2-dimethoxyethane, 2-methoxyethyl ether, ethyl acetate, glycol, N,N-dimethyl formamide, or a combination thereof.