Fluorinated aromatics

Process for preparing compounds of the formula (VI)

• 16
• where
• R1 is in each case independently C1-C12-alkyl, free or protected formyl, chlorine or bromine or a radical of the formulae (IIa) or (IIb)
• A-B-D-E (IIa) A-E (IIb)
• where, each independently,
• A is absent or is a C1-C8-alkylene radical and
• B is absent or is oxygen, sulphur or NR2
• where R2 is hydrogen or C1-C8-alkyl and
• D is a carbonyl group and
• E is C1-C8-alkyl, C1-C8-alkoxy, NH(C1-C8-alkyl) or N(C1-C8-alkyl)2 or is a cyclic amino radical having 4 to 12 carbon atoms and
• n is an integer of 0 to 4-m and
• RF is fluorine, C1-C12-fluoroalkyl, —O(C1-C12-fluoroalkyl) or —S(C1-C12-fluoroalkyl) and
• m is an integer of 1 to 3 and
• R5 is in each case independently hydrogen, C1-C12-alkyl, C2-C12-alkenyl, C5-C14-aryl or C6-C15-arylalkyl,
• comprising reacting compounds of the formula (IV)
• 17
• where R1 and RF, and also m and n, are as defined above and
• R3 and R4 are each independently C1-C8-alkyl, or NR3R4 as a whole is a cyclic amino radical having a total of 4 to 12 carbon atoms with compounds of the formula (V)
• R5CO—O—OCR5 (V)
• where the R5 radicals are as defined above.

Process for preparing compounds of the formula (IV)

• 18
• where
• R1 is in each case independently C1-C12-alkyl, free or protected formyl, chlorine or bromine or a radical of the formulae (IIa) or (IIb)
• A-B-D-E (IIa) A-E (IIb)
• where, each independently,
• A is absent or is a C1-C8-alkylene radical and
• B is absent or is oxygen, sulphur or NR2
• where R2 is hydrogen or C1-C8-alkyl and
• D is a carbonyl group and
• E is C1-C8-alkyl, C1-C8-alkoxy, NH(C1-C8-alkyl) or N(C1-C8-alkyl)2 or is a cyclic amino radical having 4 to 12 carbon atoms and
• n is an integer of 0 to 4-m and
• RF is fluorine, C1-C12-fluoroalkyl, —O(C1-C12-fluoroalkyl) or —S(C1-C12-fluoroalkyl) and
• m is an integer of 1 to 3 and
• R3 and R4 are each independently C1-C8-alkyl, or NR3R4 as a whole is a cyclic amino radical having a total of 4 to 12 carbon atoms,
• comprising converting compounds of the formula (II)
• 19
• where R1 and RF, and also n and m, are as defined above
• in the presence of formaldehyde and
• in the presence of secondary amines of the formula (III)
• HNR3R4 (III)
• where R3 and R4 are as defined above.

Compounds of the formula (I)

• 20
• where
• R1 is in each case independently C1-C12-alkyl, free or protected formyl, chlorine or bromine or a radical of the formulae (IIa) or (IIb)
• A-B-D-E (IIa) A-E (IIb)
• where, each independently,
• A is absent or is a C1-C8-alkylene radical and
• B is absent or is oxygen, sulphur or NR2
• where R is hydrogen or C1-C8-alkyl and
• D is a carbonyl group and
• E is C1-C8-alkyl, C1-C8-alkoxy, NH(C1-C8-alkyl) or N(C1-C8-alkyl)2 or is a cyclic amino radical having 4 to 12 carbon atoms and
• n is an integer of 0 to 4-m and
• RF is fluorine, C1-C12-fluoroalkyl, —O(C1-C12-fluoroalkyl) or —S(C1-C12-fluoroalkyl) and
• m is an integer of 1 to 3.

Compounds of the formula (IV)

• 21
• where
• R1 is in each case independently C1-C12-alkyl, free or protected formyl, chlorine or bromine or a radical of the formulae (IIa) or (IIb)
• A-B-D-E (IIa) A-E (IIb)
• where, each independently,
• A is absent or is a C1-C8-alkylene radical and
• B is absent or is oxygen, sulphur or NR2
• where R2 is hydrogen or C1-C8-alkyl and
• D is a carbonyl group and
• E is C1-C8-alkyl, C1-C8-alkoxy, NH(C1-C8-alkyl) or N(C1-C8-alkyl)2 or is a cyclic amino radical having 4 to 12 carbon atoms and
• n is an integer of 0 to 4-m and
• RF is fluorine, C1-C12-fluoroalkyl, —O(C1-C12-fluoroalkyl) or —S(C1-C12-fluoroalkyl) and
• m is an integer of 1 to 3 and
• R3 and R4 are each independently C1-C8-alkyl, or NR3R4 as a whole is a cyclic amino radical having a total of 4 to 12 carbon atoms,
• with the exception of 2-hydroxy-5-fluoro-N,N-dimethylbenzylamine.

Compounds of the formula (VI)

• 22
• where
• R1 is in each case independently C1-C12-alkyl, free or protected formyl, chlorine or bromine or a radical of the formulae (IIa) or (IIb)
• A-B-D-E (IIa) A-E (IIb)
• where, each independently,
• A is absent or is a C1-C8-alkylene radical and
• B is absent or is oxygen, sulphur or NR2
• where R2 is hydrogen or C1-C8-alkyl and
• D is a carbonyl group and
• E is C1-C8-alkyl, C1-C8-alkoxy, NH(C1-C8-alkyl) or N(C1-C8-alkyl)2 or is a cyclic amino radical having 4 to 12 carbon atoms and
• n is an integer of 0 to 4-m and
• RF is fluorine, C1-C12-fluoroalkyl, —O(C1-C12-fluoroalkyl) or —S(C1-C12-fluoroalkyl) and
• m is an integer of 1 to 3 and
• R5 is in each case independently hydrogen, C1-C12-alkyl, C2-C12-alkenyl, C5-C14-aryl or C6-C15-arylalkyl, with the exception of 2-acetoxy-5-fluorobenzyl acetate.

Compounds of the formula (VIIIa)

• 23
• where
• R1 is in each case independently C1-C12-alkyl, free or protected formyl, chlorine or bromine or a radical of the formulae (IIa) or (IIb)
• A-B-D-E (IIa) A-E (IIb)
• where, each independently,
• A is absent or is a C1-C8-alkylene radical and
• B is absent or is oxygen, sulphur or NR2
• where R2 is hydrogen or C1-C8-alkyl and
• D is a carbonyl group and
• E is C1-C8-alkyl, C1-C8-alkoxy, NH(C1-C8-alkyl) or N(C1-C8-alkyl)2 or is a cyclic amino radical having 4 to 12 carbon atoms and
• n is an integer of 0 to 4-m and
• RF is fluorine, C1-C12-fluoroalkyl, —O(C1-C12-fluoroalkyl) or —S(C1-C12-fluoroalkyl) and
• m is an integer of 1 to 3 and
• R6 is C1-C12-alkyl, C5-C14-aryl or C6-C15-arylalkyl.