Process for the preparation of 2-methoxymethy1-1,4-benzenediamine, its derivatives thereof and the salts thereof
A process for synthesizing 2-methoxymethyl-1,4-benzenediamine, its derivatives of formula (IV) and the salts thereof, which comprises a reductive amination step. The preferred final product is 2-methoxymethyl-1,4-benzenediamine of formula (IV-a). These compounds may be used as primary intermediates in compositions for dyeing keratin fibers.
1. A process for the preparation 1,4-diamino-2-methoxymethylbenzene (IV-a), its derivatives of formula (IV), and the salts thereof comprising the steps of:
(a) inserting a nitroso function to compounds of formula (II) in the presence of a nitrosation agent and one or more solvents to prepare compounds of formula (III)
(b) performing a reductive amination of compounds of formula (III) in the presence of an amine reducing agent, a reductive amination catalyst and one or more solvents to prepare compounds of formula (IV):
wherein R 1 , R 2 , R 3 are substituents independently selected from the group consisting of:
(a) C-linked substituents selected from the group consisting of:
(i) mono- or poly-substituted or unsubstituted, straight or branched, aliphatic, heteroaliphatic,
(ii) mono- or poly-substituted or unsubstituted, mono- or poly-unsaturated aryl systems, and
(iii) mono- or poly-substituted or unsubstituted, mono- or poly-unsaturated heteroaryl systems, and
wherein said systems of (i), (ii) and (iii) comprise from about 1 to 10 carbon atoms and from about 0 to 5 heteroatoms selected from the group consisting of O, F, N, P and Si;
(b) S-linked substituents selected from the group consisting of SA 1 , SO 2 A 1 , SO 3 A 1 , SSA 1 , SOA 1 , SO 2 NA 1 A 2 , SNA 1 A 2 , and SONA 1 A 2 ;
(c) O-linked substituents selected from the group consisting of OA 1 , ONA 1 A 2 ;
(d) N-linked substituents selected from the group consisting of NA 1 A 2 ; (NA 1 A 2 A 3 ) + , NA 1 SA 2 , NO 2 ; NA 1 A 2 ;
(e) substituents selected from the group consisting of COOA 1 , CONA 1 , CONA 1 COA 2 , C(═NA 1 )NA 1 A 2 , CN, and X;
(f) fluoroalkyl substituents selected from the group consisting of mono-, poly-, and per-fluoro alkyl systems comprising from 1 to 12 carbon atoms and from 0 to 4 heteroatoms; and
(g) H;
and mixtures thereof;
wherein A 1 , A 2 , and A 3 are substituents independently selected from the group consisting of H; substituted or unsubstituted, straight or branched, alkyl, mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinic systems; substituted or unsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclic systems; and substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl systems, or A 1 and A 2 together with nitrogen atoms to which they are bound form a ring; wherein said systems comprise from 1 to 10 carbon atoms and from 0 to 5 heteroatoms selected from the group consisting of O, S, N, P, and Si; and wherein X is a halogen selected from the group consisting of F, Cl, Br, I, and mixtures thereof;
wherein R 4 is a substituent independently selected from the group consisting of a hydrogen, mono- or poly-substituted or unsubstituted, straight or branched, aliphatic, heteroaliphatic and mixtures thereof;
wherein R 5 is a substituent independently selected from the group consisting of a hydrogen, mono- or poly-substituted or unsubstituted, straight or branched, aliphatic, heteroaliphatic and mixtures thereof;
wherein R 6 and R 7 is selected from the group consisting of hydrogen, hydroxyl, alkyl, hereo alkyl, mono or poly-hydroxyalkyl, mono or poly-hydroxy hetero alkyl;
wherein n is equal to 0, 1, 2, or 3.
2. A process according to claim 1 further comprising the step of alkylating compounds of formula (I) in the presence of an alkylating agent and one or more solvents to prepare compounds of formula (II),
wherein R 1 , R 2 , R 3 , R 4 are substituents and n is an indicia as defined in claim 1 ; and
wherein R 5′ is a substituent independently selected from the group consisting of a mono- or poly-substituted or unsubstituted, straight or branched, aliphatic, heteroaliphatic and mixtures thereof.
3. A process according to claim 1 further comprising the step of transforming of compound (IV) into a salt of the formula (VII) in presence of an acid mHZ and one more solvents:
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are substituents and n is an indicia as defined in claim 1 .
4. A process according to claim 3 , wherein the acid HZ is selected from the group consisting of D,L-malic acid, L-malic, D-malic, hydrochloric, hydrobromic, citric, acetic, lactic, succinic, tartaric, or sulfuric acids and mixtures thereof and m=1 or 2.
5. A process according to claim 2 , wherein the steps of b) nitrosation and c) reductive amination and a) alkylating, are performed successively in this order.
6. A process according to claim 2 , wherein the steps of a) alkylating, b) nitrosation and c) reductive amination steps are performed successively in this order.
7. A process according to claim 2 , wherein the alkylating agent is a nucleophilic alkylating agent or an electrophilic alkylating agent.
8. A process according according to claim 1 , wherein the reductive amination step c) comprises the two successive steps of:
performing a condensation step d) by reacting compounds of formula (III) in presence of an amine R 6 R 7 NH and one or more solvents to prepare compounds of formula (VI):
wherein R 6 and R 7 is selected from the group consisting of hydrogen, hydroxyl, alkyl, hereo alkyl, mono or poly-hydroxyalkyl, mono or poly-hydroxy hetero alkyl;
wherein R 1 , R 2 , R 3 , R 4 , R 5 are substituents and n is an indicia as defined in claim 1 ; and subsequently
performing a reductive step e) by reacting compounds of formula (VI) in presence of a reducing agent, and optionally a reductive amination catalyst and one or more solvents to prepare compounds of formula (IV):
wherein R 6 and R 7 is selected from the group consisting of hydrogen, hydroxyl, alkyl, hereo alkyl, mono or poly-hydroxyalkyl, mono or poly-hydroxy hetero alkyl;
wherein R 1 , R 2 , R 3 , R 4 , R 5 are substituents and n is an indicia as defined in claim 1 .
9. A process according to claim 8 , wherein the reducing agent comprises hydrazine, H 2 , LiAlH 4 , LiBH 4 , DiBAl, NaBH 4 , NaCNBH 3 , B 2 H 6 , sodium hydrosulfite, sodium sulfide, and mixtures of thereof.
10. A process according to claim 8 , wherein the reductive amination catalyst is selected from the group consisting of Raney nickel, nickel, palladium, Lindlar catalyst, cobalt, copper chromite, platinium, platinum oxide, rhenium, tin(II) chloride, titanium(III) chloride, zinc, samarium, iron and mixtures thereof.
11. A process for making 2-methoxymethyl-benzene-1,4-diamine comprising the steps of:
a) methylating 2-hydroxymethyl-phenol (I-a) in methanol to prepare 2-methoxymethyl-phenol (II-a);
wherein Me represents a methyl group;
b) inserting a nitroso function to 2-methoxymethyl-phenol (II-a) in presence of a source of nitroso function and one or more solvents to prepare 2-methoxymethyl[1,4]-benzoquinone 4-oxime (III-a);
wherein Me represents a methyl group;
d) performing a condensation step by reacting 2-methoxymethyl[1,4]-benzoquinone 4-oxime (III-a) with hydroxylamine, in presence of a base and one or more solvents to prepare 2-methoxymethyl-[1,4]-benzoquinone dioxime (VI-a); and
wherein Me represents a methyl group;
e) performing a reductive step by reacting 2-methoxymethyl[1,4]-benzoquinone dioxime (VI-a) in presence of a reducing agent and reductive amination catalyst and one or more solvents to prepare 2-methoxymethyl-benzene-1,4-diamine (IV-a);
wherein Me represents a methyl group.
12. A process according to claim 11 , wherein the methylation step a) is performed at a temperature from 0° C. to 200° C.
13. A process according to claim 11 , wherein the source of nitroso function of the nitrosation step b) is NaNO 2 and H 2 SO 4 .
14. A process according to claim 11 , wherein the nitrosation step b) is performed at acidic pH, wherein the pH range is from 1 to 4.
15. A process according to claim 11 , wherein the solvent of the nitrosation step b) is selected from the group consisting of pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol and mixtures thereof.
16. A process according to claim 11 , wherein the nitrosation step b) is performed at 0° C.
17. A process according to claim 11 , wherein in the reductive step e) the reducing agent is hydrazine, and the reductive amination catalyst is Raney Nickel.
18. A process according to claim 11 , wherein the solvent of the reductive step e) is selected from the group consisting of pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, methyl-tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, n-butanol, isopropanol, n-propanol, ethanol, methanol and mixtures thereof.
19. A process according to claim 11 , wherein the reduction step e) is performed at 25° C.