Process for the synthesis of n-alkoxyamines

A process for the preparation of a sterically hindered amine ether of the formula (100)

• wherein
• G1 and G2 are independently C1-C4alkyl;
• R2 is C3-C18alkyl or C5-C12cycloalkyl;
• T1 is hydroxy, —NT2T3, —OT22, T20 or a group of formula (102);
• T2 is hydrogen, C5-C12cycloalkyl or R42;
• or T2 is R42 substituted by C1-C18alkoxy, aryl, hydroxy, carboxy, —CO—O—R42, or —O—CO—R42;
• T3 is hydrogen, C5-C12cycloalkyl, R42, aryl, -Q-NHT2 or -Q-NT2T21;
• or T3 is R42 substituted by C1-C18alkoxy, aryl, hydroxy, carboxy, —CO—O—R42, or —O—CO—R42;
• or T3 is aryl substituted by C1-C18alkoxy, aryl, hydroxy, carboxy, —CO—O-—R42, —O—CO—R42 or halogen;
• or T2 and T3 form together C4-C11alkylene or C4-C11alkylene substituted by C1-C18alkoxy, aryl, hydroxy, carboxy, —CO—O—R42, or —O—CO—R42;
• with the proviso that T2 and T3 are not benzyl;
• R42 is C1-C18alkyl;
• Q is C2-C18alkylene, C5-C12cycloalkylene or phenylene;
• T22 is —(CO)—(C1-C16alkylene)0 or 1-(CO)—O-T21;
• T21 IS
• T20 is
• R30 is R42 or R42 substituted by hydroxy;
• or R30 is —(CH2)n—NT23-(CH2)p—NT23-(CH2)n—NHT23 with one T23 substituent being hydrogen and two T23 substituents being
• n is 1 to 4;
• p is 1 to 3;
• the group of formula (102) is
• y is 2 to 20;
• which comprises transforming a compound of formula (101),
• wherein
• R1 is C3-C18alkenyl or C5-C12cycloalkenyl,
• in one reaction step in the presence of hydrogen and a catalyst into a compound of formula (100) wherein T1 is hydroxy or —NT2T3;
• whereby for obtaining compounds with T1=—NT2T3 the transformation is performed in the presence of an amine of formula HNT2T30;
• T30 is hydrogen, C5-C12cycloalkyl, R42, aryl or -Q-NHT2;
• or T30 is R42 substituted by C1-C18alkoxy, aryl, hydroxy, carboxy, —CO—O—R42, or —O—CO—R42;
• or T30 is aryl substituted by C1-C18alkoxy, aryl, hydroxy, carboxy, —CO—O—R42, —O—CO—R42 or halogen;
• or T2 and T30 form together C4-C11alkylene or C4-C11alkylene substituted by C1-C18alkoxy, aryl, hydroxy, carboxy, —CO—O—R42, or —O—CO—R42;
• with the proviso that T30 is not benzyl;
• and for obtaining a compound of formula (100) with T1=—OT22, reacting a compound of formula (100) with T1=hydroxy with an HOOC—(C1-C16alkylene)0 or 1-COOH or a halide thereof or a methyl ester thereof;
• for obtaining a compound of formula (100) with T1=T20, and R30=R42 substituted by hydroxy, reacting a compound of formula (100) with T1=—NT2T3, T2=H, T3=R42 with a cyanuric halide to yield a compound of formula (103), which is subsequently reacted with R42NH2 or hydroxy-substituted R42NH2;
• wherein
• X is halogen;
• for obtaining a compound of formula (100) with T1=T20 and R30=—(CH2), NT23-(CH2)p—NT23-(CH2)n—NHT23,
• a compound of formula (103) is reacted with H2N—(CH2)n—NH—(CH2)p—NH—(CH2)n—NH2;
• and
• for obtaining a compound of formula (100) with T1=group of formula (102), reacting a compound of formula (100) with T1=—NT2T3, T2=H, T3=R42, with a cyanuric halide to yield a compound of formula (104),
• which is subsequently reacted with a compound of formula (100) with T1=—NT2T3, T2=H, T3=-Q-NHT21, to yield a compound of formula (105),
• which is subsequently reacted with a compound of formula (100) with T1=—NT2T3, T2=H, T3=-Q-NHT21, to yield a compound of formula (106),
• which is subsequently reacted with a compound 2-X-4,6-bis((R42)2-amino)-s-triazine