Process for the production of meso-substituted cyanine dyes
A single-step process for the production of meso-substituted cyanine dyes is provided comprising the reaction of a dye (III), with (a) a methylene compound (IV) or (V) or a quaternary salt (VI) or (VII) and (b) a compound selected from functionalized (hetero)aromatic compounds Ar—B, saturated cyclic amines (IV) and heteroaromatic compounds (V).
1 - 14 . (canceled)
15 . A process for the production of a meso-substituted cyanine dye represented by formulas (I) or (II)
wherein
each R 1 is independently —COOH, —SO 3 H, a hydrogen atom, optionally substituted C 1 -C 12 alkyl, halogen, optionally substituted C 1 -C 12 alkoxy, —NO 2 , —CN, or fused aromatic or heteroaromatic ring systems,
each X is independently —CR 3 ═CR 4 —, —O—, —S—, —NR 6 — or —CR 5 2 —,
each R 2 is optionally substituted C 1 -C 12 alkyl, optionally substituted aryl, —(C 1 -C 12 alkanediyl)-SO 3 H or —(C 1 -C 12 alkanediyl-)COOH,
each R 2a is optionally substituted C 1 -C 12 alkyl, optionally substituted aryl, —(C 1 -C 12 alkanediyl)-SO 3 − , —(C 1 -C 12 alkanediyl)-COO 31 or —(C 1 -C 12 alkanediyl)-NR 6 3 + ,
each R 3 and R 4 are independently —COOH, —SO 3 H, —COOR 6 , —CN, —NO 2 , —OH, —NR 6 2 , a hydrogen atom, optionally substituted C 1 -C 12 alkyl, optionally substituted C 1 -C 12 alkoxy, halogen or aryl,
R 5 is independently C 1 -C 12 alkyl,
Z − is Cl − , Br − , I − , SCN − , PF 6 − , SbF 6 − , AsF 6 − , aryl-SO 3 − , alkyl-O—SO 3 − ,
PO 4 H 2 − , CH 3 SO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − , HSO 4 − , BF 4 − or ClO 4 − ,
n is 0 if R 2a is —(C 1 -C 12 alkanediyl)- SO 3 − or —(C 1 -C 1 alkanediyl)-COO − ,
n is 1 if R 2a is optionally substituted C 1 -C 12 alkyl or aryl,
n is 2 if R 2a is —(C 1 -C 12 alkanediyl)-NR 6 3 + ,
Y is —S—Ar, —Se—Ar—, —O—Ar, —NR 6 —Ar, —SO 2 —Ar or —(N-heterocycle),
R 6 is a hydrogen atom or optionally substituted C 1 -C 12 alkyl,
Ar is an aromatic group wherein one or more ring carbon atoms are optionally replaced by N, O or S heteroatoms, and the fragment
represents C 2 -C 3 alkanediyl, optionally substituted with substituents that are the same or different selected from the grouping consisting of one or more C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl and halogen atoms,
said process comprising the single-step reaction in an inert organic solvent miscible with water of:
(a) a dye of formula (III)
wherein A is Cl or Br and the fragment
is as defined above for formulas (I) and (II), with
(b) a compound comprising:
(i) a methylene derivative of formulas (IV) or (V)
(ii) a quaternary salt of formulas (VI) or (VII),
wherein X, R 1 , R 2 , R 3 , R 4 and Z − are as defined in formulas (I) and (II), and
(c) a compound C comprising:
(i) aromatic and heteroaromatic functionalized compounds Ar—B,
(ii) saturated 5- or 6-membered cyclic amines
(iii) 5- or 6-membered heteroaromatic compounds
comprising at least one nitrogen atom as heteroatom in the aromatic ring, which nitrogen atom is bonded to the two adjacent ring carbon atoms via a single and a double bond and comprises a free electron pair
wherein
Ar represents 5- or 6-membered aryl, wherein one or more ring carbon atoms are optionally replaced by N, O or S heteroatoms,
B is —NHR 6 , —SH, —OH, —SeH or —SO 2 H,
R 6 is a hydrogen atom or optionally substituted C 1 -C 12 alkyl, and the saturated cyclic amines optionally comprise an additional N, O or S heteroatom in the ring.
16 . The process according to claim 15 , wherein the dye (III) is reacted with at least one methylene compound (IV) or at least one quaternary salt (VI) and a compound C, and a cyanine dye of formula (I) is obtained.
17 . The process according to claim 15 , wherein the dye (III) is reacted with at least one methylene compound (V) or at least one quaternary salt (VII) and a compound C, and a cyanine dye of formula (II) is obtained.
18 . The process according to claim 15 , wherein the fragment
—CH 2 -CH 2 — or —CH 2 -CH 2 -CH 2 —.
19 . The process according to claim 15 , wherein Y is —S—Ar.
20 . The process according to claim 15 , wherein only one methylene derivative or quaternary salt is used and a dye with a symmetrical structure of formulas (I) or (II) is obtained.
21 . The process according to claim 15 , wherein the compound C and the dye (III) are provided in a reaction vessel and the methylene compound of formulas (IV) or (V) or the quaternary salt of formulas (VI) or (VII) is added in dissolved form.
22 . The process according to claim 15 , wherein an alkali hydroxide is added to the reaction mixture if B is —SH, —OH, —SeH or —SO 2 H.
23 . The process according to claim 15 , wherein a quaternary salt of formulas (VI) or (VII) is used and an amount of a base equimolar to the amount of quaternary salt is added to the reaction mixture.
24 . The process according to claim 15 , wherein the cyanine dye of formulas (I) or (II) is precipitated by the addition of a mineral acid.
25 . The process according to claim 15 , wherein compound C is a aromatic and heteroaromatic functionalized compounds Ar—B.
26 . The process according to claim 15 , wherein compound C is 5- or 6-membered heteroaromatic compounds
comprising at least one nitrogen atom as heteroatom in the aromatic ring, which nitrogen atom is bonded to the two adjacent ring carbon atoms via a single and a double bond and comprises a free electron pair wherein
Ar represents 5- or 6-membered aryl, wherein one or more ring carbon atoms are optionally replaced by N, O or S heteroatoms,
B is —NHR 6 , —SH, —OH, —SeH or —SO 2 H,
R 6 is a hydrogen atom or optionally substituted C 1 -C 12 alkyl, and the saturated cyclic amines optionally comprise an additional N, O or S heteroatom in the ring.
27 . The process according to claim 15 , wherein the cyanine dye of formulas (I) or (II) is subsequently subjected to an extraction.
28 . The process according to claim 15 , wherein the cyanine dye of formulas (I) or (II) is subjected to an anion exchange.