Ortho-substituted pentafluorosulfanylbenzenes, process for their preparation and their use as valuable synthetic intermediates
View Patent ↗Pentafluorosulfanyl-benzenes according to Formula (I): a process for their preparation and their use as valuable synthetic intermediates for preparing, for example, medicaments, diagnostic aids, liquid crystals, polymers, pesticides, herbicides, fungicides, nematicides, parasiticides, insecticides, acaricides and arthropodicides.
1. A compound of Formula I:
wherein:
R1 is:
(a) Cl, Br, I, —CN, —SO 2 R6, NO 2 , alkoxy having 1 to 4 carbon atoms, NR7R8, —O—(CH 2 ) b —(CF 2 ) c —CF 3 , —(SO d ) e —(CH 2 ) f —(CF 2 ) g —CF 3 , alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 8 carbon atoms, wherein 1 to 4 hydrogen atoms in said cycloalkyl may be replaced by fluorine, atoms; where a, b and c are, each independently, 0 to 1, d is 0 to 2, e is 0 to 1, f is 0 to 4 and g is 0 to 1; and where
R6 is OH, F, Cl, Br, I or alkyl having 1 to 4 carbon atoms; and
R7 and R8 are, each independently, —CH 2 —CF 3 , hydrogen, or alkyl having 1 to 4 carbon atoms; or
(b) —CH 2 ) h -phenyl or —O-phenyl, wherein the phenyl radicals are unsubstituted or substituted by 1 to 3 radicals selected, each independently, from the group consisting of F, Cl, Br, I, —O j —(CH 2 ) k —CF 3 , —SO 2 CH 3 , alkoxy having 1 to 4 carbon atoms, and alkyl having 1 to 4 carbon atoms, where j is 0 to 1, k is 0 to 3, and h is 0 to 4; or
(c) —(CH 2 ) l -heteroaryl which is unsubstituted or substituted by 1 to 3 radicals selected, each independently, from the group consisting of F, Cl, Br, I, —O m —(CH 2 ) n —CF 3 , —SO 2 CH 3 alkoxy having 1, to 4 carbon atoms, and alkyl having 1 to 4 carbon atoms, where m is 0 to 1, n is 0 to 3, and l is 0 to 4;
R2 and R4 are, each independently, hydrogen, F, Cl, Br, I, —CN, NR9R10, —OR11, —SR12, —COR13, —SO q CH 3 , —(SO r ) s —(CH 2 ) t —(CF 2 ) u —CF 3 , alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 8 carbon atoms in said alkyl or cycloalkyl may be replaced by fluorine atoms, where q and r are, each independently, 1 to 2, s is 0 to 1, t is 0 to 4, u is 0 to 1; and where
R9 and R10:
(a) are each independently, —(CH 2 ) v —(CF 2 ) w —CF 3 , alkyl having 1 to 4 carbon atoms, alkylcarbonyl having 1to 4 carbon atoms, or alkylsulfonyl having 1 to 4 carbon atoms, where v is 0 to 4 and w is 0 to 1; or
(b) together with the nitrogen atom bearing them, form a heterocycle of Formula (III):
where X and Y are, each independently, CO or SO 2 ; and where R11 and R12 are each independently, —(CH 2 ) v —(CF 2 ) w —CF 3 , hydrogen, alkyl having 1 to 4 carbon atoms, alkylcarbonyl having 1to 4 carbon atoms, or alkylsulfonyl having 1 to 4 carbon atoms where v is 0 to 4 and w is 0 to 1; and R13 is OH, alkyl having 1 to 6 carbon atoms or alkoxy having 1to 6 carbon atoms;
R3 is hydrogen, F, Cl, Br, I, CN, —NO 2 , —COR14, —SO 2 CH 3 , alkyl having 1 to 6 carbon atoms, alkoxy having 1to 4 carbon atoms, or —O x —(CH 2 ) y —CF 3 , where x is 0 to 1 and y is 0 to 3; and where R14 is OH, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms or —O aa —(CH 2 ) bb —CF 3 , where aa is 0 to 1 and bb is 0 to 3;
R5 is:
(a) hydrogen, F, Cl, Br, I, —CN, —SO 2 CH 3 , NR15R16, —O—(CH 2 ) ee —(CF 2 ) ff —CF 3 , —(SO gg ) hh —(CH 2 ) jj —(CF 2 ) kk —CF 3 , alkoxy having 1to 4 carbon atoms, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 8 carbon atoms, where 1 to 4 hydrogen atoms in said alkyl or cycloalkyl may be replaced by fluorine atoms, where ee and ff are, each independently, 0 to 1, gg is 0 to 2, hh is 0 to 1, jj is 0 to 4, kk is 0 to 1; and where
R15 and R16 are, each independently, hydrogen, —CH 2 —CF 3 , alkyl having 1 to 4 carbon atoms; or
(b) —(CH 2 ) ll -phenyl or —O-phenyl wherein the phenyl radicals are unsubstituted or substituted by 1 to 3 radicals selected, each independently, from the group consisting of F, Cl, Br, I, —SO 2 CH 3 , —O mm —(CH 2 ) nn —CF 3 , alkoxy having 1 to 4 carbon atoms, or alkyl having 1to 4 carbon atoms, where mm is 0 to 1, nn is 0 to 3, and ll is 0 to 4; or
(c) —(CH 2 ) oo -heteroaryl which is unsubstituted or substituted by 1 to 3 radicals selected, each independently, from the group consisting of F, Cl, Br, I, —SO 2 CH 3 , —O pp —(CH 2 ) rr —CF 3 , alkoxy having 1 to 4 carbon atoms or alkyl having 1 to 4 carbon atoms, where pp is 0 to 1, rr is 0 to 3, and oo is 0 to 4;
or a salt of a compound of Formula (I), excluding compounds of Formula (I) and the corresponding salts wherein, in the same molecule:
R2 and R4 are each Cl and R3 is F or Cl;
R2 and R4 are either Cl or CN, wherein R2 and R4 have a total of one Cl and one CN substituent, and R3 is Cl; or
R1 is NO 2 and the other substituents are each hydrogen.
2. The compound of claim 1 , wherein:
R1 is:
(a) Cl, Br, I, —CN, —SO 2 R6, NO 2 alkoxy having 1to 4 carbon atoms, NR7R8, —O—(CH 2 ) b —(CF 2 ) c —CF 3 , —(SO d ) e —(CH 2 ) f —(CF 2 ) g —CF 3 , alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 8 carbon atoms, wherein 1 to 4 hydrogen atoms in said alkyl or cycloalkyl may be replaced by fluorine atoms; where a, b and c are, each independently, 0 to 1, d is 0 to 2, e is 0 to 1, f is 0 to 4, and g is 0 to 1; and where
R6 is OH, F, Cl, Br, I or alkyl having 1 to 4 carbon atoms; and
R7 and R8 are, each independently, —CH 2 —CF 3 , hydrogen, or alkyl having 1 to 4 carbon atoms; or
(b) —(CH 2 ) h -phenyl or —O-phenyl, wherein the phenyl radicals are unsubstituted or substituted by 1 to 3 radicals selected, each independently, from the group consisting of F, Cl, Br, I, —O j —(CH 2 ) k —CF 3 , —SO 2 CH 3 , alkyl having 1 to 4 carbon atoms, and alkyl having 1 to 4 carbon atoms, where j is 0 to 1, k is 0 to 3, and h is 0 to 4; or
(c) —(CH 2 ) l -heteroaryl which is unsubstituted or substituted by 1 to 3 radicals selected, each independently, from the group consisting of F, Cl, Br, I, —O m —(CH 2 ) n —CF 3 , —SO 2 CH 3 , alkoxy having 1 to 4 carbon atoms, and alkyl having 1 to 4 carbon atoms, where m is 0 to 1, n is 0 to 3, and 1 is 0 to 4;
R2 and R4 are, each independently, hydrogen, F, Cl, Br, I, —CN, NR9R10, —OR11, —SR12, —COR13, —(SO r ) s —(CH 2 ) t —(CF 2 ) u —CF 3 , alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 8 carbon atoms, wherein 1 to 4 hydrogen atoms in said alkyl or cycloalkyl may be replaced by fluorine atoms, where r is 1 to 2, s is 0 to 1, t is 0 or 1, u is 0 or 1; and where
R9 and R10:
(a) are each independently, —(CH 2 ) v —(CF 2 ) w —CF 3 , alkyl having 1 to 4 carbon atoms, alkylcarbonyl having 1 to 4 carbon atoms, or alkylsulfonyl having 1 to 4 carbon atoms, where v is 0 or 1 and w is 0 to 1; or
(b) together with the nitrogen atom bearing them, form a heterocycle of Formula (III):
where X and Y are, each independently, CO or SO 2 ; and where
R11 and R12 are, each independently, —(CH 2 ) v —(CF 2 ) w —CF 3 , hydrogen, alkyl having 1 to 4 carbon atoms, alkylcarbonyl having 1 to 4 carbon atoms, or alkylsulfonyl having 1 to 4 carbon atoms where v is 0 or 1 and w is 0 or 1; and
R13 is OH, alkyl having 1 to 6 carbon atoms or alkoxy having 1 to 6 carbon atoms;
R3 is hydrogen, F, Cl, Br, I, —CN, —NO 2 , —COR14, —SO 2 CH 3 , alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 4 carbon atoms, or —O x —(CH 2 ) y —CF 3 , where x is 0 to 1 and y is 0 to 3; and where
R14 is OH, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms or —O aa —(CH 2 ) bb —CF 3 , where aa is 0 to 1 and bb is 0 to 3;
R5 is:
a) hydrogen, F, Cl, Br, I, —CN, —SO 2 CH 3 , NR15R16, —O—(CH 2 ) ee —(CF 2 ) ff —CF 3 , —(SO gg ) hh —(CH 2 ) jj —(CF 2 ) kk —CF 3 , alkoxy having 1 to 4 carbon atoms, alkyl having 1 to 6 carbon atoms or eye cycloalkyl having 3 to 8 carbon atoms, where 1 to 4 hydrogen atoms in said alkyl or cycloalkyl may be replaced by fluorine atoms, where ee and ff are, each independently. 0 to 1, gg is 0 to 2, hh is 0 to 1, jj is 0 to 4, kk is 0 to 1;
and where
R15 and R16 are, each independently, hydrogen, —CH 2 —CF 3 , alkyl having 1 to 4 carbon atoms; or
(b) —(CH 2 ) ll -phenyl or —O-phenyl, wherein the phenyl radicals are unsubstituted or substituted by 1 to 3 radicals selected, each independently, from the group consisting of F, Cl, Br, I, —SO 2 CH 3 , —O mm —(CH 2 ) nn —CF 3 , alkoxy having 1 to 4 carbon atoms, or alkyl having 1 to 4 carbon atoms, where mm is 0 to 1, nn is 0 to 3, and ll is 0 to 4; or
(c) —(CH 2 ) o o-heteroaryl which is unsubstituted or substituted by 1 to 3 radicals selected, each independently, from the group consisting of F, Cl, Br, I, —SO 2 CH 3 , —O pp —(CH 2 ) rr —CF 3 , alkoxy having 1 to 4 carbon atoms or alkyl having 1 to 4 carbon atoms, where pp is 0 to 1, rr is 0 to 3, and oo is 0 to 4;
or a salt of a compound of Formula (I), excluding compounds of Formula (I) and the corresponding salts wherein, in the same molecule:
R2 and R4 are each Cl and R3 is F or Cl;
R2 and R4 are either Cl or CN, wherein R2 and R4 have a total of one Cl and one CN substituent, and R3 is Cl; or
R1 is NO 2 and the other substituents are each hydrogen.
3. The compound of claim 1 , wherein:
R1 is Cl, Br, I, —SO 2 R6 or NO 2 ; and where
R6 is OH, F, Cl, Br, I or alkyl having 1 to 4 carbon atoms;
R2 and R4 are, each independently, hydrogen, F, Cl, Br, I, —CN, NR9R10, —OR11, —SR12, —COR13, —(SO r ) s —(CH 2 ) t —(CF 2 ) u —CF 3 , alkyl having 1 to 6 carbon atoms, or cycloalkyl having 3 to 8 carbon atoms, wherein 1 to 4 hydrogen atoms in said alkyl or cycloalkyl may be replaced by fluorine atoms, where r is 1 to 2, s is 0 to 1, t is 0 or 1, u is 0 or 1; and where
R9 and R10:
(a) are each independently, —(CH 2 ) v —(CF 2 ) w —CF 3 , alkyl having 1 to 4 carbon atoms, alkylcarbonyl having 1 to 4 carbon atoms, or alkylsulfonyl having 1 to 4 carbon atoms, where v is 0 or 1 and w is 0 or 1; or
(b) together with the nitrogen atom bearing them, form a heterocyclo of Formula (IIIa):
R11 and R12 are, each independently, —(CH 2 ) v —(CF 2 ) w —CF 3 , hydrogen, alkyl having 1 to 4 carbon atoms, alkylcarbonyl having 1 to 4 carbon atoms, or alkylsulfonyl having 1 to 4 carbon atoms where v is 0 or 1 and w is 0 or 1; and
R13 is OH, alkyl having 1 to 6 carbon atoms or alkoxy having 1 to 6 carbon atoms;
R3 is hydrogen, F, Cl, Br, I, —CN, —NO 2 , —COR14, —SO 2 CH 3 , alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 4 carbon atoms, or —O x —(CH 2 ) y —CF 3 , where x is 0 or 1 and y is 0 to 3; and where
R14 is OH, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms or —O aa —(CH 2 ) bb —CF 3 , where aa is 0 to 1 and bb is 0 to 3;
R5 is:
(a) hydrogen, F, Cl, Br, I, —CN, —SO 2 CH 3 , NR15R16, —O—(CH 2 ) ee —(CF 2 ) ff —CF 3 , —(SO gg ) hh —(CH 2 ) jj —(CF 2 ) kk —CF 3 , alkoxy having 1 to 4 carbon atoms, alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 8 carbon atoms, where 1 to 4 hydrogen atoms in said alkyl or cycloalkyl may be replaced by fluorine atoms, where ee and ff are, each independently, 0 to 1, gg is 0 to 2, hh is 0 to 1, jj is 0 to 4, kk is 0 to 1; and where
R15 and R16 are, each independently, hydrogen, —CH 2 —CF 3 , alkyl having 1 to 4 carbon atoms; or
(b) —(CH 2 ) ll -phenyl or —O-phenyl, wherein the phenyl radicals are unsubstituted or substituted by 1 to 3 radicals selected, each independently, from the group consisting of F, Cl, Br, I, —SO 2 CH 3 , —O mm —(CH 2 ) nn —CF 3 , alkoxy having 1 to 4 carbon atoms, or alkyl having 1 to 4 carbon atoms, where mm is 0 to 1, nn is 0 to 3, and ll is 0 to 4; or
(c) —(CH 2 ) oo -heteroaryl which is unsubstituted or substituted by 1 to 3 radicals selected, each independently, from the group consisting of F, Cl, Br, I, —SO 2 CH 3 , —O pp —(CH 2 ) rr —CF 3 , alkoxy having 1 to 4 carbon atoms or alkyl having 1 to 4 carbon atoms, where pp is 0 to 1, rr is 0 to 3, and oo is 0 to 4;
and salts thereof; excluding compounds of Formula (I) wherein, in the same molecule:
R2 and R4 are each Cl and R3 is F or Cl;
one of the R2 and R4 substituents is Cl and the other of the R2 and R4 substituents is CN and R3 is Cl; and
R1 is NO 2 and the other substituents are each hydrogen.