U.S. patent application number 14/084830 was filed with the patent office on 2015-05-21 for fused ring indeno compounds for preparation of photochromic compounds.
This patent application is currently assigned to Transitions Optical, Inc.. The applicant listed for this patent is Transitions Optical, Inc.. Invention is credited to Meng He, Anil Kumar, Massimiliano Tomasulo.
Application Number | 20150141663 14/084830 |
Document ID | / |
Family ID | 52014367 |
Filed Date | 2015-05-21 |
United States Patent
Application |
20150141663 |
Kind Code |
A1 |
He; Meng ; et al. |
May 21, 2015 |
Fused Ring Indeno Compounds For Preparation Of Photochromic
Compounds
Abstract
The present invention relates to intermediate compounds
represented by the following Formula (I-A), ##STR00001## The
intermediate compounds of the present invention, such as
represented by Formula (I-A), can be used to prepare photochromic
compounds, such as photochromic fused ring indenopyran compounds,
including but not limited to photochromic fused ring
indeno-naphtho-pyran compounds.
Inventors: |
He; Meng; (Murrysville,
PA) ; Tomasulo; Massimiliano; (Monroeville, PA)
; Kumar; Anil; (Murrysville, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Transitions Optical, Inc. |
Pinellas Park |
FL |
US |
|
|
Assignee: |
Transitions Optical, Inc.
Pinellas Park
FL
|
Family ID: |
52014367 |
Appl. No.: |
14/084830 |
Filed: |
November 20, 2013 |
Current U.S.
Class: |
548/418 ;
549/234 |
Current CPC
Class: |
C07C 49/507 20130101;
C07D 209/70 20130101; C07D 307/93 20130101; C07D 307/89 20130101;
C07C 49/747 20130101; G02B 5/23 20130101; C07C 2603/54 20170501;
C09K 19/36 20130101; C09K 19/32 20130101; C09K 2019/3408 20130101;
C07D 307/77 20130101; C09K 19/3491 20130101; C09K 19/3488 20130101;
C07D 307/88 20130101; C07C 50/36 20130101; C07D 311/78 20130101;
C07D 209/94 20130101; C07D 311/94 20130101; C09K 19/60 20130101;
C09K 9/02 20130101; C07C 2603/52 20170501 |
Class at
Publication: |
548/418 ;
549/234 |
International
Class: |
C07D 307/93 20060101
C07D307/93; C07D 209/94 20060101 C07D209/94 |
Claims
1. An intermediate compound for preparation of a photochromic
compound, wherein said intermediate compound is represented by the
following Formula (I-A), ##STR00031## wherein, Ring-A is selected
from aryl and fused ring aryl, n is selected from 1 to 8, R.sup.1
for each n is in each case independently selected from hydrogen,
hydrocarbyl and substituted hydrocarbyl each optionally and
independently interrupted with at least one of --O--, --S--,
--C(O)--, --C(O)O--, --S(O)--, --SO.sub.2--, --N.dbd.N--,
--N(R.sub.11')-- where R.sub.11' is selected from hydrogen,
hydrocarbyl or substituted hydrocarbyl,
--Si(OR.sub.8').sub.w(R.sub.8').sub.t--, where w and t are each
independently selected from 0 to 2, provided that the sum of w and
t is 2, and each R.sub.8' is independently selected from hydrogen,
hydrocarbyl and substituted hydrocarbyl, and combinations of two or
more thereof; halogen; cyano; --O--R.sub.10' or --S--R.sub.10' or
--C(O)--R.sub.10' or --C(O)--OR.sub.10', wherein each R.sub.10' is
independently selected from hydrogen, hydrocarbyl or substituted
hydrocarbyl; perhalohydrocarbyl; and
--C(O)--N(R.sub.11')(R.sub.12') or --N(R.sub.11')R.sub.12', wherein
R.sub.11' and R.sub.12' are each independently selected from
hydrogen, hydrocarbyl or substituted hydrocarbyl, or R.sub.11' and
R.sub.12' together form a ring structure optionally including at
least one heteroatom, R.sup.2 and R.sup.3 are each independently
selected from hydrogen, hydrocarbyl, substituted hydrocarbyl,
halogen, --C(O)--N(R.sub.14)(R.sub.15), --N(R.sub.14)(R.sub.15),
--SR.sub.16, and --OR.sub.16, where R.sub.14 and R.sub.15 are each
independently selected from hydrogen, hydrocarbyl, and substituted
hydrocarbyl, or R.sub.14 and R.sub.15 together form a ring, and
each R.sub.16 is independently selected from hydrocarbyl and
substituted hydrocarbyl, R.sup.4 and R.sup.5 are each independently
selected from hydrogen, hydrocarbyl, and substituted hydrocarbyl,
each optionally and independently interrupted with --O--, --S--,
--N(R.sub.11')--, where R.sub.11' is selected from hydrogen,
hydrocarbyl or substituted hydrocarbyl, R.sup.6 is selected from
hydrogen, --C(O)--R.sub.19 and --S(O)(O)R.sub.19, wherein R.sub.19
is selected from hydrocarbyl and halohydrocarbyl, Z.sub.1 and
Z.sub.3 are each independently selected from O, C(O) and
C(R.sub.a)(R.sub.b), where R.sub.a and R.sub.b are each
independently selected from hydrogen, hydroxyl, and
C.sub.1-C.sub.20 linear or branched alkyl, provided that at least
one of Z.sub.1 and Z.sub.3 is C(O), and Z.sub.2 is selected from O,
S, divalent hydrocarbyl, and N--R.sub.13, where R.sub.13 is
selected from hydrogen, hydrocarbyl and substituted hydrocarbyl
each optionally and independently interrupted with at least one of
--O--, --S--, --C(O)--, --C(O)O--, --S(O)--, --SO.sub.2--,
--N.dbd.N--, --N(R.sub.11')-- where R.sub.11' is selected from
hydrogen, hydrocarbyl or substituted hydrocarbyl,
--Si(OR.sub.8').sub.w(R.sub.8').sub.t--, where w and t are each
independently selected from 0 to 2, provided that the sum of w and
t is 2, and each R.sub.8' is independently selected from hydrogen,
hydrocarbyl and substituted hydrocarbyl, and combinations of two or
more thereof, or Z.sub.2 defines an optionally substituted fused
ring.
2. The intermediate compound of claim 1 wherein, Ring-A, for
Formula (I-A), is selected from aryl; R.sup.1, for Formula (I-A),
for each n is independently selected from, hydrogen, halogen
selected from fluoro, bromo, iodo, and chloro; C.sub.1-C.sub.20
linear or branched alkyl; C.sub.3-C.sub.10 cycloalkyl; substituted
or unsubstituted phenyl, the phenyl substituents being selected
from halogen, halo(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20 alkyl
or C.sub.1-C.sub.20 alkoxy; --O--R.sub.10' or --S--R.sub.10',
wherein each R.sub.10' independently is hydrogen, C.sub.1-C.sub.20
alkyl, phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkyl
substituted phenyl(C.sub.1-C.sub.20)alkyl,
mono(C.sub.1-C.sub.20)alkoxy substituted
phenyl(C.sub.1-C.sub.20)alkyl,
(C.sub.1-C.sub.20)alkoxy(C.sub.2-C.sub.20)alkyl, C.sub.3-C.sub.10
cycloalkyl, or mono(C.sub.1-C.sub.20)alkyl substituted
C.sub.3-C.sub.10 cycloalkyl; --N(R.sub.11')R.sub.12' or
--C(O)--N(R.sub.11')(R.sub.12'), wherein R.sub.11' and R.sub.12'
are each independently hydrogen, C.sub.1-C.sub.20 alkyl, phenyl,
naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,
benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl,
benzopyridyl, fluorenyl, C.sub.1-C.sub.20 alkylaryl,
C.sub.3-C.sub.10 cycloalkyl, C.sub.4-C.sub.20 bicycloalkyl,
C.sub.5-C.sub.20 tricycloalkyl or C.sub.1-C.sub.20 alkoxyalkyl,
wherein said aryl group is phenyl or naphthyl, or R.sub.11' and
R.sub.12' come together with the nitrogen atom to form a
C.sub.3-C.sub.20 hetero-bicycloalkyl ring or a C.sub.4-C.sub.20
hetero-tricycloalkyl ring; a nitrogen containing ring represented
by the following graphic formula XIIA, ##STR00032## wherein each
--Y-- is independently chosen for each occurrence from --CH.sub.2-,
--CH(R.sub.13')--, --C(R.sub.13').sub.2--, --CH(aryl)-,
--C(aryl).sub.2-, and --C(R.sub.13')(aryl)-, and Z is --Y--, --O--,
--S--, --NH--, --N(R.sub.13')--, or --N(aryl)-, wherein each
R.sub.13' is independently C.sub.1-C.sub.20 alkyl, each aryl is
independently phenyl or naphthyl, m is an integer 1, 2 or 3, and p
is an integer 0, 1, 2, or 3 and provided that when p is 0, Z is
--Y--; a group represented by one of the following graphic formulas
XIIB or XIIC, ##STR00033## wherein R.sub.15, R.sub.16, and R.sub.17
are each independently hydrogen, C.sub.1-C.sub.20 alkyl, phenyl, or
naphthyl, or the groups R.sub.15 and R.sub.16 together form a ring
of 5 to 8 carbon atoms and each R.sup.d is independently for each
occurrence selected from C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20
alkoxy, fluoro or chloro, and Q is an integer 0, 1, 2, or 3; and
unsubstituted, mono-, or di-substituted C.sub.4-C.sub.18
spirobicyclic amine, or unsubstituted, mono-, and di-substituted
C.sub.4-C.sub.18 spirotricyclic amine, wherein said substituents
are independently aryl, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20
alkoxy, or phenyl(C.sub.1-C.sub.20)alkyl; or two adjacent R.sup.1
groups together form a group represented by one of XIID and XIIE:
##STR00034## wherein T and T' are each independently oxygen or the
group --NR.sub.11'--, where R.sub.11', R.sub.15, and R.sub.16 are
as set forth above; R.sup.2 and R.sup.3, for Formula (I-A), are
each independently selected from, hydrogen, halogen selected from
F, Cl, Br, and I, C.sub.1-C.sub.20 linear or branched alkyl;
C.sub.3-C.sub.10 cycloalkyl; substituted or unsubstituted phenyl,
the phenyl substituents being selected from halogen, hydroxyl,
halo(C.sub.1-C.sub.20)alkyl, carbonyl, C.sub.1-C.sub.20
alkoxycarbonyl, cyano, C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20
alkoxy; --C(O)N(R.sub.14)(R.sub.15) or --N(R.sub.14)(R.sub.15),
where R.sub.14 and R.sub.15 are each independently selected from,
hydrogen, C.sub.1-C.sub.20 linear or branched alkyl;
C.sub.3-C.sub.10 cycloalkyl; and substituted or unsubstituted
phenyl, the phenyl substituents being selected from halogen,
halo(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy; or R.sub.14 and R.sub.15 together form a
ring; and --OR.sub.16, or --SR.sub.16, where each R.sub.16 is
independently selected from, C.sub.1-C.sub.20 linear or branched
alkyl; C.sub.3-C.sub.10 cycloalkyl; and substituted or
unsubstituted phenyl, the phenyl substituents being selected from
halogen, halo(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy; R.sup.4 and R.sup.5, for Formula (I-A),
are each independently selected from, (i) hydrogen,
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 haloalkyl,
C.sub.3-C.sub.10 cycloalkyl, allyl, benzyl, or mono-substituted
benzyl, said benzyl substituents being chosen from halogen,
C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 alkoxy; (ii) an
unsubstituted, mono- di- or tri-substituted group chosen from
phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl,
benzofuranyl, thienyl, benzothienyl, dibenzofuranyl,
dibenzothienyl, carbazolyl, or indolyl, said group substituents in
each case being independently chosen from halogen, C.sub.1-C.sub.20
alkyl or C.sub.1-C.sub.20 alkoxy; (iii) mono-substituted phenyl,
said substituent located at the para position being
--(CH.sub.2).sub.t-- or --O--(CH.sub.2).sub.t--, wherein t is the
integer 1, 2, 3, 4, 5 or 6, said substituent being connected to an
aryl group which is a member of a photochromic material; and (iv)
the group --CH(R.sup.10)G, wherein R.sup.10 is hydrogen,
C.sub.1-C.sub.6 alkyl or the unsubstituted, mono- or di-substituted
aryl groups phenyl or naphthyl, and G is --CH.sub.2OR.sup.11,
wherein R.sup.11 is hydrogen, C.sub.1-C.sub.20 alkyl,
C.sub.1-C.sub.20 alkoxy(C.sub.1-C.sub.20)alkyl,
phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkoxy
substituted phenyl(C.sub.1-C.sub.20)alkyl, or the unsubstituted,
mono- or di-substituted aryl groups phenyl or naphthyl, each of
said phenyl and naphthyl group substituents being C.sub.1-C.sub.20
alkyl or C.sub.1-C.sub.20 alkoxy; or (v) R.sup.4 and R.sup.5
together form a spiro substituent selected from a substituted or
unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon
atoms, a substituted or unsubstituted spiro-heterocyclic ring
containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including
the spirocarbon atom, said spiro-carbocyclic ring and
spiro-heterocyclic ring being annellated with 0, 1 or 2 benzene
rings, said substituents being hydrogen or C.sub.1-C.sub.20 alkyl;
and R.sup.6 for Formula (I-A) is selected from hydrogen,
--C(O)--R.sub.19 and --S(O)(O)R.sub.19, wherein R.sub.19 is
selected from C.sub.1-C.sub.20 linear or branched alkyl and
C.sub.1-C.sub.20 linear or branched perfluoroalkyl.
3. The intermediate compound of claim 2 wherein, Ring-A, for
Formula (I-A), is C.sub.6-aryl, R.sup.1, for Formula (I-A), for
each n is independently selected from hydrogen, C.sub.1-C.sub.6
linear or branched alkyl, C.sub.3-C.sub.7 cycloalkyl,
C.sub.1-C.sub.8 haloalkyl, fluoro, bromo, iodo, chloro, and
--O--R.sub.10', R.sup.2 and R.sup.3, for Formula (I-A), are each
independently selected from hydrogen, C.sub.1-C.sub.6 linear or
branched alkyl; C.sub.3-C.sub.7 cycloalkyl; and substituted or
unsubstituted phenyl, the phenyl substituents being selected from
halogen, halo(C.sub.1-C.sub.6)alkyl, C.sub.1-C.sub.6 alkyl or
C.sub.1-C.sub.6 alkoxy; R.sup.4 and R.sup.5, for Formula (I-A), are
each independently selected from hydrogen, C.sub.1-C.sub.8 alkyl,
C.sub.1-C.sub.8 haloalkyl, and C.sub.3-C.sub.7 cycloalkyl, or
R.sup.4 and R.sup.5 together form a spiro substituent selected from
a substituted or unsubstituted spiro-carbocyclic ring containing 3
to 6 carbon atoms; and R.sup.6 for Formula (I-A) is selected from
--C(O)--R.sub.19 and --S(O)(O)R.sub.19, wherein R.sub.19 is
selected from C.sub.1-C.sub.10 linear or branched alkyl and
C.sub.1-C.sub.10 linear or branched perfluoroalkyl.
4. The intermediate compound of claim 1 wherein, Z.sub.2 is
N--R.sub.13, and R.sub.13 is a group L represented by the following
Formula (II), and optionally at least one R.sup.1 independently for
each n, is selected from said group L represented by the following
Formula (II),
--[S.sub.1].sub.c-[Q.sub.1-[S.sub.2].sub.d].sub.d'-[Q.sub.2-[S.sub.3].sub-
.e].sub.e'-[Q.sub.3-[S.sub.4].sub.f].sub.f'--S.sub.5--P Formula
(II) wherein: (a) Q.sub.1, Q.sub.2, and Q.sub.3 for each
occurrence, are independently selected from a divalent group
selected from optionally substituted aryl, optionally substituted
heteroaryl, optionally substituted cycloalkyl, and optionally
substituted heterocycloalkyl; wherein the aryl substituents,
heteroaryl substituents, cycloalkyl substituents, and
heterocycloalkyl substituents are each independently selected from
P, liquid crystal mesogens, halogen, poly(C.sub.1-C.sub.18 alkoxy),
C.sub.1-C.sub.18 alkoxycarbonyl, C.sub.1-C.sub.18 alkylcarbonyl,
C.sub.1-C.sub.18 alkoxycarbonyloxy, aryloxycarbonyloxy,
perfluoro(C.sub.1-C.sub.18)alkoxy,
perfluoro(C.sub.1-C.sub.18)alkoxycarbonyl,
perfluoro(C.sub.1-C.sub.18)alkylcarbonyl,
perfluoro(C.sub.1-C.sub.18)alkylamino,
di-(perfluoro(C.sub.1-C.sub.18)alkyl)amino,
perfluoro(C.sub.1-C.sub.18)alkylthio, C.sub.1-C.sub.18 alkylthio,
C.sub.1-C.sub.18 acetyl, C.sub.3-C.sub.10 cycloalkyl,
C.sub.3-C.sub.10 cycloalkoxy, straight-chain C.sub.1-C.sub.18
alkyl, and branched C.sub.1-C.sub.18 alkyl; wherein said
straight-chain C.sub.1-C.sub.18 alkyl and branched C.sub.1-C.sub.18
alkyl are mono-substituted with a group selected from cyano,
halogen, and C.sub.1-C.sub.18 alkoxy; or wherein said
straight-chain C.sub.1-C.sub.18 alkyl and branched C.sub.1-C.sub.18
alkyl are poly-substituted with at least two groups independently
selected from halogen, -M(T).sub.(v-1) and -M(OT).sub.(v-1),
wherein M is chosen from aluminum, antimony, tantalum, titanium,
zirconium and silicon, T is chosen from organofunctional radicals,
organofunctional hydrocarbon radicals, aliphatic hydrocarbon
radicals and aromatic hydrocarbon radicals, and v is the valence of
M; (b) c, d, e, and f are each independently chosen from an integer
of 1 to 20; and each S.sub.1, S.sub.2, S.sub.3, S.sub.4, and
S.sub.5 is independently chosen for each occurrence from a spacer
unit selected from: (i) optionally substituted alkylene, optionally
substituted haloalkylene, --Si(CH.sub.2).sub.g--, and
--(Si[(CH.sub.3).sub.2]O).sub.h--, wherein g for each occurrence is
independently chosen from an integer from 1 to 20; h for each
occurrence is independently chosen from an integer from 1 to 16;
and said substitutes for the alkylene and haloalkylene are
independently selected from C.sub.1-C.sub.18 alkyl,
C.sub.3-C.sub.10 cycloalkyl and aryl; (ii) --N(Z)--,
--C(Z).dbd.C(Z)--, --C(Z).dbd.N--, --C(Z').sub.2--C(Z').sub.2--,
and a single bond, wherein Z for each occurrence is independently
selected from hydrogen, C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.10
cycloalkyl and aryl, and Z' for each occurrence is independently
selected from C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.10 cycloalkyl
and aryl; and (iii) --O--, --C(.dbd.O)--, --C.ident.C--,
--N.dbd.N--, --S--, --S(.dbd.O)--, --(O.dbd.)S(.dbd.O)--,
--(O.dbd.)S(.dbd.O)O--, --O(O.dbd.)S(.dbd.O)O-- and straight-chain
or branched C.sub.1-C.sub.24 alkylene residue, said
C.sub.1-C.sub.24 alkylene residue being unsubstituted,
mono-substituted by cyano or halogen, or poly-substituted by
halogen, provided that when two spacer units comprising heteroatoms
are linked together the spacer units are linked so that heteroatoms
are not directly linked to each other, the bond between R.sub.13
and the nitrogen atom of N--R.sub.13 is free of two heteroatoms
linked to each other, and the bond between S.sub.5 and P is free of
two heteroatoms linked to each other; (c) P for each occurrence is
independently selected from hydroxy, amino, C.sub.2-C.sub.18
alkenyl, C.sub.2-C.sub.18 alkynyl, azido, silyl, siloxy,
silylhydride, (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato,
thioisocyanato, acryloyloxy, methacryloyloxy,
2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl,
aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylic
ester, acryloylamino, methacryloylamino, aminocarbonyl,
C.sub.1-C.sub.18 alkyl aminocarbonyl,
aminocarbonyl(C.sub.1-C.sub.18)alkyl, C.sub.1-C.sub.18
alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl,
hydroxy(C.sub.1-C.sub.18)alkyl, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.18 alkoxy, amino(C.sub.1-C.sub.18)alkyl,
C.sub.1-C.sub.18alkylamino, di-(C.sub.1-C.sub.18)alkylamino,
C.sub.1-C.sub.18 alkyl(C.sub.1-C.sub.18)alkoxy, C.sub.1-C.sub.18
alkoxy(C.sub.1-C.sub.18)alkoxy, nitro, poly(C.sub.1-C.sub.18)alkyl
ether,
(C.sub.1-018)alkyl(C.sub.1-C.sub.18)alkoxy(C.sub.1-C.sub.18)alkyl,
polyethyleneoxy, polypropyleneoxy, ethylene, acryloyl,
acryloyloxy(C.sub.1-C.sub.18)alkyl, methacryloyl,
methacryloyloxy(C.sub.1-C.sub.18)alkyl, 2-chloroacryloyl,
2-phenylacryloyl, acryloyloxyphenyl, 2-chloroacryloylamino,
2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano,
isocyanato(C.sub.1-C.sub.18)alkyl, itaconic acid ester, vinyl
ether, vinyl ester, a styrene derivative, main-chain and side-chain
liquid crystal polymers, siloxane derivatives, ethyleneimine
derivatives, maleic acid derivatives, maleimide derivatives,
fumaric acid derivatives, unsubstituted cinnamic acid derivatives,
cinnamic acid derivatives that are substituted with at least one of
methyl, methoxy, cyano and halogen, and substituted or
unsubstituted chiral or non-chiral monovalent or divalent groups
chosen from steroid radicals, terpenoid radicals, alkaloid radicals
and mixtures thereof, wherein the substituents are independently
chosen from C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkoxy, amino,
C.sub.3-C.sub.10 cycloalkyl, C.sub.1-C.sub.18
alkyl(C.sub.1-C.sub.18)alkoxy, fluoro(C.sub.1-C.sub.18)alkyl,
cyano, cyano(C.sub.1-C.sub.18)alkyl, cyano(C.sub.1-C.sub.18)alkoxy
or mixtures thereof, or P is a structure having from 2 to 4
reactive groups, or P is an unsubstituted or substituted ring
opening metathesis polymerization precursor, or P is a substituted
or unsubstituted photochromic compound; and (d) d', e' and f' are
each independently chosen from 0, 1, 2, 3, and 4, provided that the
sum of d'+e'+f' is at least 1.
5. The intermediate compound of claim 4 wherein, for said group L
represented by Formula (II), (a) Q.sub.1, Q.sub.2, and Q.sub.3 for
each occurrence, are independently selected from optionally
substituted aryl and optionally substituted cycloalkyl, (b) each
S.sub.1, S.sub.2, S.sub.3, S.sub.4, and S.sub.5 is independently
chosen for each occurrence from a spacer unit selected from, (ii)
--N(Z)--, --C(Z).dbd.C(Z)--, --C(Z).dbd.N--,
--C(Z').sub.2--C(Z').sub.2--, and a single bond, wherein Z for each
occurrence is independently selected from hydrogen, C.sub.1-C.sub.8
alkyl, C.sub.3-C.sub.6 cycloalkyl and aryl, and Z' for each
occurrence is independently selected from C.sub.1-C.sub.8 alkyl,
C.sub.3-C.sub.6cycloalkyl and aryl, and (iii) --O--, --C(.dbd.O)--,
--C.ident.C--, --N.dbd.N--, --S--, --S(.dbd.O)--, and
straight-chain or branched C.sub.1-C.sub.12 alkylene residue, said
C.sub.1-C.sub.12 alkylene residue being unsubstituted,
mono-substituted by cyano or halogen, or poly-substituted by
halogen, and (c) P for each occurrence is independently selected
from hydrogen, hydroxy, amino, C.sub.2-C.sub.8 alkenyl,
C.sub.2-C.sub.8 alkynyl, acryloyloxy, methacryloyloxy,
2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl,
epoxy, carboxylic acid, carboxylic ester, acryloylamino,
methacryloylamino, aminocarbonyl, C.sub.1-C.sub.8 alkyl
aminocarbonyl, aminocarbonyl(C.sub.1-C.sub.8)alkyl, C.sub.1-C.sub.8
alkyloxycarbonyloxy, halocarbonyl, aryl,
hydroxy(C.sub.1-C.sub.8)alkyl, C.sub.1-C.sub.8 alkyl,
C.sub.1-C.sub.8 alkoxy, amino(C.sub.1-C.sub.8)alkyl,
C.sub.1-C.sub.8 alkylamino, di-(C.sub.1-C.sub.8)alkylamino,
C.sub.1-C.sub.8 alkyl(C.sub.1-C.sub.8)alkoxy, C.sub.1-C.sub.8
alkoxy(C.sub.1-C.sub.8)alkoxy, nitro, poly(C.sub.1-C.sub.8)alkyl
ether,
(C.sub.1-C.sub.8)alkyl(C.sub.1-C.sub.8)alkoxy(C.sub.1-C.sub.8)alkyl,
polyethyleneoxy, polypropyleneoxy, ethylene, acryloyl,
acryloyloxy(C.sub.1-C.sub.18)alkyl, methacryloyl,
methacryloyloxy(C.sub.1-C.sub.8)alkyl, 2-chloroacryloyl,
2-phenylacryloyl, acryloyloxyphenyl, 2-chloroacryloylamino,
2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano,
isocyanato(C.sub.1-C.sub.18)alkyl, itaconic acid ester, vinyl
ether, and vinyl ester.
6. The intermediate compound of claim 5 wherein, for said group L
represented by Formula (II), (b) each S.sub.1, S.sub.2, S.sub.3,
S.sub.4, and S.sub.5 is independently chosen for each occurrence
from a spacer unit selected from, (ii) --N(Z)--, --C(Z).dbd.C(Z)--,
and a single bond, wherein Z for each occurrence is independently
selected from hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.3-C.sub.6
cycloalkyl and aryl, and (iii) --O--, --O(.dbd.O)--, --C.ident.C--,
and straight-chain or branched C.sub.1-C.sub.6 alkylene residue,
said C.sub.1-C.sub.6 alkylene residue being unsubstituted,
mono-substituted by cyano or halogen, or poly-substituted by
halogen, and (c) P for each occurrence is independently selected
from hydrogen, hydroxy, amino, C.sub.2-C.sub.8 alkenyl,
C.sub.2-C.sub.8 alkynyl, and aryl.
7. The intermediate compound of claim 6 wherein Z.sub.1 and Z.sub.3
are each C(O).
8. The intermediate compound of claim 1 wherein, said intermediate
compound represented by Formula (I-A) is represented by the
following Formula (I-B), ##STR00035##
9. The intermediate compound of claim 4 wherein each group L is
independently selected from, ##STR00036## ##STR00037## ##STR00038##
##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043##
##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048##
provided that R.sub.13 of N--R.sub.13 is only selected from L(5),
L(6), L(7), L(8), L(9), L(12), L(14), L(21), L(24), L(27), L(34),
L(36), L(h), L(i), L(j), L(l), L(m), L(n), L(n), L(o), L(p), L(u),
L(v), L(w), L(ac), L(ae), L(af), L-DC-(a), L-DC-(b), L-DC-(c),
L-DC-(d), L-DC-(e), L-DC-(h), L-DC-(i), and L-DC-(l).
10. The intermediate compound of claim 8 wherein said intermediate
compound represented by Formula (I-B) is selected from at least one
of: ##STR00049## ##STR00050## ##STR00051## ##STR00052##
##STR00053## ##STR00054##
Description
FIELD
[0001] The present invention relates to fused ring indeno compounds
that are used as intermediate compounds in the preparation of
photochromic compounds.
BACKGROUND
[0002] Fused ring indeno compounds, such as fused ring indeno
naphthols and fused ring indeno naphtha-esters, have many uses,
such as intermediates in the synthesis of photochromic compounds
and materials, such as indeno-fused ring pyrans, including
indeno-fused naphthopyrans. Photochromic materials, such as
indeno-fused naphthopyrans, in response to certain wavelengths of
electromagnetic radiation (or "actinic radiation"), typically
undergo a transformation from one form or state to another form,
with each form having a characteristic or distinguishable
absorption spectrum associated therewith. Typically, upon exposure
to actinic radiation, many photochromic materials are transformed
from a closed-form, which corresponds to an unactivated (or
bleached, or substantially colorless) state of the photochromic
material, to an open-form, which corresponds to an activated (or
colored) state of the photochromic material. In the absence of
exposure to actinic radiation, such photochromic materials are
reversibly transformed from the activated (or colored) state, back
to the unactivated (or bleached) state. Compositions and articles,
such as eyewear lenses, that contain photochromic materials or have
photochromic materials applied thereto (such as in form of a
photochromic coating composition) typically display colorless (or
clear) and colored states that correspond to the colorless and
colored states of the photochromic materials contained therein
and/or applied thereto.
[0003] Fused ring indeno compounds, such as indeno-fused naphthol
materials are typically prepared by a synthetic scheme involving
the reaction of a benzophenone with a dialkyl succinate, which is
typically referred to as a Stobbe reaction route. Such known
methods can be limited with regard to the types of groups, such as
precursor groups and lengthening groups, and the ring-positions of
such groups on the resulting fused ring indeno compounds. The
introduction of groups at various ring positions can involve
additional synthetic steps, and in some instances reduced product
yields due in some cases to additional isolation steps.
[0004] Some photochromic materials, such as photochromic
indeno-fused naphthopyrans can be expensive, and in light of
economic considerations, reducing the costs associated with
synthesizing such materials is typically desirable.
[0005] It would be desirable to develop fused ring indeno
compounds, such as fused ring indeno naphtho-esters and fused ring
indeno naphthols, that can be used to prepare photochromic
compound. In addition, it would be desirable that such newly
developed intermediate compounds have or allow for the introduction
of certain groups, at ring-positions that are not possible or
readily obtainable with presently available intermediate
compounds.
SUMMARY
[0006] In accordance with the present invention, there is provided
an intermediate compound for preparation of a photochromic
compound, wherein the intermediate compound is represented by the
following Formula (I-A),
##STR00002##
[0007] With reference to the intermediate compound represented by
Formula (I-A), which can be described as a fused ring indeno
compound, Ring-A is selected from aryl and fused ring aryl, and n
is selected from 1 to 8.
[0008] With reference to Formula (I-A), R.sup.1 for each n is in
each case independently selected from hydrogen, hydrocarbyl and
substituted hydrocarbyl each optionally and independently
interrupted with at least one of --O--, --S--, --C(O)--, --C(O)O--,
--S(O)--, --SO.sub.2--, --N.dbd.N--, --N(R.sub.11')-- where
R.sub.11' is selected from hydrogen, hydrocarbyl or substituted
hydrocarbyl, --Si(OR.sub.8').sub.w(R.sub.8').sub.t--, where w and t
are each independently selected from 0 to 2, provided that the sum
of w and t is 2, and each R.sub.8' is independently selected from
hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations
of two or more thereof; halogen; cyano; --O--R.sub.10' or
--S--R.sub.10' or --C(O)--R.sub.10' or --C(O)--OR.sub.10', wherein
each R.sub.10' is independently selected from hydrogen, hydrocarbyl
or substituted hydrocarbyl; perhalohydrocarbyl; and
--C(O)--N(R.sub.11')(R.sub.12') or --N(R.sub.11')R.sub.12', wherein
R.sub.11' and R.sub.12' are each independently selected from
hydrogen, hydrocarbyl or substituted hydrocarbyl, or R.sub.11' and
R.sub.12' together form a ring structure optionally including at
least one heteroatom.
[0009] With additional reference to Formula (I-A), R.sup.2 and
R.sup.3 are each independently selected from hydrogen, hydrocarbyl,
substituted hydrocarbyl,
halogen, --C(O)--N(R.sub.14)(R.sub.15), --N(R.sub.14)(R.sub.15),
--SR.sub.16, and --OR.sub.16, where R.sub.14 and R.sub.15 are each
independently selected from hydrogen, hydrocarbyl, and substituted
hydrocarbyl, or R.sub.14 and R.sub.15 together form a ring, and
each R.sub.16 is independently selected from hydrocarbyl and
substituted hydrocarbyl.
[0010] With further additional reference to Formula (I-A), R.sup.4
and R.sup.5 are each independently selected from hydrogen,
hydrocarbyl, and substituted hydrocarbyl, each optionally and
independently interrupted with --O--, --S--, --N(R.sub.11')--,
where R.sub.11' is selected from hydrogen, hydrocarbyl or
substituted hydrocarbyl.
[0011] With still further reference to Formula (I-A), R.sup.6 is
selected from hydrogen, --C(O)--R.sub.19 and --S(O)(O)R.sub.19,
wherein R.sub.19 is selected from hydrocarbyl and
halohydrocarbyl.
[0012] With still additional reference to Formula (I-A), Z.sub.1
and Z.sub.3 are each independently selected from O, C(O) and
C(R.sub.a)(R.sub.b), where R.sub.a and R.sub.b are each
independently selected from hydrogen, hydroxyl, and
C.sub.1-C.sub.20 linear or branched alkyl, provided that at least
one of Z.sub.1 and Z.sub.3 is C(O).
[0013] With still further additional reference to Formula (I-A),
Z.sub.2 is selected from O, S, divalent hydrocarbyl, and
N--R.sub.13, where R.sub.13 is selected from hydrogen, hydrocarbyl
and substituted hydrocarbyl each optionally and independently
interrupted with at least one of --O--, --S--, --C(O)--, --C(O)O--,
--S(O)--, --SO.sub.2--, --N.dbd.N--, --N(R.sub.11')-- where
R.sub.11' is selected from hydrogen, hydrocarbyl or substituted
hydrocarbyl, --Si(OR.sub.8').sub.w(R.sub.8').sub.t--, where w and t
are each independently selected from 0 to 2, provided that the sum
of w and t is 2, and each R.sub.8' is independently selected from
hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations
of two or more thereof, or Z.sub.2 defines an optionally
substituted fused ring.
[0014] The features that characterize the present invention are
pointed out with particularity in the claims, which are annexed to
and form a part of this disclosure. These and other features of the
invention, its operating advantages and the specific objects
obtained by its use will be more fully understood from the
following detailed description in which non-limiting embodiments of
the invention are illustrated and described.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is an illustrative representative general scheme,
Scheme-(1), of a method for preparing the intermediate compound of
the present invention;
[0016] FIG. 2 is an illustrative representative scheme, Scheme-(2),
of a method for preparing the intermediate compound of the present
invention;
[0017] FIG. 3 is an illustrative representative scheme, Scheme-(3),
of a method for preparing the intermediate compound of the present
invention;
[0018] FIG. 4 is an illustrative representative scheme, Scheme-(4),
of various equilibriums by which structural isomers of the lactone
compounds represented by Formulas (III-A') and (III-A'') are
converted from one to the other;
[0019] FIG. 5 is an illustrative representative scheme, Scheme-(5),
of a method of preparing a lactone compound that is used, with some
embodiments, to prepare the intermediate compound of the present
invention; and
[0020] FIG. 6 is an illustrative representative scheme, Scheme-(6),
of a method of preparing an acid ester precursor of the lactone
compound depicted in Scheme-(5).
[0021] In FIGS. 1-6 like characters refer to the same compounds,
reactants, and/or groups as the case may be, unless otherwise
stated.
DETAILED DESCRIPTION
[0022] As used herein, the articles "a," "an," and "the" include
plural referents unless otherwise expressly and unequivocally
limited to one referent.
[0023] As used herein, the intermediate compound of the present
invention is also referred to as a fused ring indeno compound and a
fused ring indeno intermediate compound.
[0024] Unless otherwise indicated, all ranges or ratios disclosed
herein are to be understood to encompass any and all subranges or
subratios subsumed therein. For example, a stated range or ratio of
"1 to 10" should be considered to include any and all subranges
between (and inclusive of) the minimum value of 1 and the maximum
value of 10; that is, all subranges or subratios beginning with a
minimum value of 1 or more and ending with a maximum value of 10 or
less, such as but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to
10.
[0025] As used herein, unless otherwise indicated, left-to-right
representations of linking groups, such as divalent linking groups,
are inclusive of other appropriate orientations, such as, but not
limited to, right-to-left orientations. For purposes of
non-limiting illustration, the left-to-right representation of the
divalent linking group
##STR00003##
or equivalently --C(O)O--, is inclusive of the right-to-left
representation thereof,
##STR00004##
or equivalently --O(O)C-- or --OC(O)--.
[0026] Other than in the operating examples, or where otherwise
indicated, all numbers expressing quantities of ingredients,
reaction conditions, and so forth used in the specification and
claims are to be understood as modified in all instances by the
term "about."
[0027] The intermediate compounds of the present invention, as
described herein, including, but not limited to, compounds
represented by Formula (I-A), Formula (I-B), and Formulas (I-B)-(1)
through (I-B)-(16) Formula (I-C), in each case optionally further
include one or more coproducts, resulting from the synthesis of
such compounds.
[0028] As used herein, the term "photochromic" and similar terms,
such as "photochromic compound" means having an absorption spectrum
for at least visible radiation that varies in response to
absorption of at least actinic radiation. Further, as used herein
the term "photochromic material" means any substance that is
adapted to display photochromic properties (such as, adapted to
have an absorption spectrum for at least visible radiation that
varies in response to absorption of at least actinic radiation) and
which includes at least one photochromic compound.
[0029] As used herein, the term "actinic radiation" means
electromagnetic radiation that is capable of causing a response in
a material, such as, but not limited to, transforming a
photochromic material from one form or state to another as will be
discussed in further detail herein.
[0030] As used herein, the term "photochromic material" includes
thermally reversible photochromic materials and compounds and
non-thermally reversible photochromic materials and compounds. The
term "thermally reversible photochromic compounds/materials" as
used herein means compounds/materials capable of converting from a
first state, for example a "clear state," to a second state, for
example a "colored state," in response to actinic radiation, and
reverting back to the first state in response to thermal energy.
The term "non-thermally reversible photochromic
compounds/materials" as used herein means compounds/materials
capable of converting from a first state, for example a "clear
state," to a second state, for example a "colored state," in
response to actinic radiation, and reverting back to the first
state in response to actinic radiation of substantially the same
wavelength(s) as the absorption(s) of the colored state (e.g.,
discontinuing exposure to such actinic radiation).
[0031] As used herein to modify the term "state," the terms "first"
and "second" are not intended to refer to any particular order or
chronology, but instead refer to two different conditions or
properties. For purposes of non-limiting illustration, the first
state and the second state of a photochromic compound can differ
with respect to at least one optical property, such as but not
limited to the absorption of visible and/or UV radiation. Thus,
according to various non-limiting embodiments disclosed herein, the
photochromic compounds of the present invention can have a
different absorption spectrum in each of the first and second
state. For example, while not limiting herein, a photochromic
compound prepared from the fused ring indeno compounds prepared by
the method of the present invention can be clear in the first state
and colored in the second state. Alternatively, a photochromic
compound prepared from the fused ring indeno compounds prepared by
the method of the present invention can have a first color in the
first state and a second color in the second state.
[0032] As used herein the term "optical" means pertaining to or
associated with light and/or vision. For example, according to
various non-limiting embodiments disclosed herein, the optical
article or element or device can be chosen from ophthalmic
articles, elements and devices, display articles, elements and
devices, windows, mirrors, and active and passive liquid crystal
cell articles, elements and devices.
[0033] As used herein the term "ophthalmic" means pertaining to or
associated with the eye and vision. Non-limiting examples of
ophthalmic articles or elements include corrective and
non-corrective lenses, including single vision or multi-vision
lenses, which can be either segmented or non-segmented multi-vision
lenses (such as, but not limited to, bifocal lenses, trifocal
lenses and progressive lenses), as well as other elements used to
correct, protect, or enhance (cosmetically or otherwise) vision,
including without limitation, contact lenses, intra-ocular lenses,
magnifying lenses, and protective lenses or visors.
[0034] As used herein the term "display" means the visible or
machine-readable representation of information in words, numbers,
symbols, designs or drawings. Non-limiting examples of display
elements include screens, monitors, and security elements, such as
security marks.
[0035] As used herein the term "window" means an aperture adapted
to permit the transmission of radiation there-through. Non-limiting
examples of windows include automotive and aircraft transparencies,
windshields, filters, shutters, and optical switches.
[0036] As used herein the term "mirror" means a surface that
specularly reflects a large fraction of incident light.
[0037] As used herein the term "liquid crystal cell" refers to a
structure containing a liquid crystal material that is capable of
being ordered. A non-limiting example of a liquid crystal cell
element is a liquid crystal display.
[0038] As used herein, spatial or directional terms, such as
"left", "right", "inner", "outer", "above", "below", and the like,
relate to the invention as it is depicted in the drawing figures.
It is to be understood, however, that the invention can assume
various alternative orientations and, accordingly, such terms are
not to be considered as limiting.
[0039] As used herein, the terms "formed over," "deposited over,"
"provided over," "applied over," residing over," or "positioned
over," mean formed, deposited, provided, applied, residing, or
positioned on but not necessarily in direct (or abutting) contact
with the underlying element, or surface of the underlying element.
For example, a layer "positioned over" a substrate does not
preclude the presence of one or more other layers, coatings, or
films of the same or different composition located between the
positioned or formed layer and the substrate.
[0040] As used herein, the term "Ring Position" means a particular
position in the ring structure, such as the fused ring structure,
of a chemical compound, such as the fused ring indeno intermediate
compounds of the present invention, and which are depicted herein
in accordance with some embodiments by numbers within the ring
structures of representative chemical formulas.
[0041] All documents, such as but not limited to issued patents and
patent applications, referred to herein, and unless otherwise
indicated, are to be considered to be "incorporated by reference"
in their entirety.
[0042] As used herein, recitations of "linear or branched" groups,
such as linear or branched alkyl, are herein understood to include:
a methylene group or a methyl group; groups that are linear, such
as linear C.sub.2-C.sub.20 alkyl groups; and groups that are
appropriately branched, such as branched C.sub.3-C.sub.20 alkyl
groups.
[0043] As used herein, recitations of "optionally substituted"
group, means a group, including but not limited to, alkyl group,
cycloalkyl group, heterocycloalkyl group, aryl group, and/or
heteroaryl group, in which at least one hydrogen thereof has been
optionally replaced or substituted with a group that is other than
hydrogen, such as, but not limited to, halo groups (e.g., F, Cl, I,
and Br), hydroxyl groups, ether groups, thiol groups, thio ether
groups, carboxylic acid groups, carboxylic acid ester groups,
phosphoric acid groups, phosphoric acid ester groups, sulfonic acid
groups, sulfonic acid ester groups, nitro groups, cyano groups,
hydrocarbyl groups (including, but not limited to: alkyl; alkenyl;
alkynyl; cycloalkyl, including poly-fused-ring cycloalkyl and
polycyclocalkyl; heterocycloalkyl; aryl, including hydroxyl
substituted aryl, such as phenol, and including poly-fused-ring
aryl; heteroaryl, including poly-fused-ring heteroaryl; and aralkyl
groups), and amine groups, such as --N(R.sub.11')(R.sub.12') where
R.sub.11' and R.sub.12' are each independently selected, with some
embodiments, from hydrogen, linear or branched C.sub.1-C.sub.20
alkyl, C.sub.3-C.sub.12 cycloakyl, C.sub.3-C.sub.12
heterocycloalkyl, aryl, and heteroaryl.
[0044] As used herein, recitations of "halo substituted" and
related terms (such as, but not limited to, haloalkyl groups,
haloalkenyl groups, haloalkynyl groups, haloaryl groups and
halo-heteroaryl groups) means a group in which at least one, and up
to and including all of the available hydrogen groups thereof is
substituted with a halo group. The term "halo-substituted" is
inclusive of "perhalo-substituted." As used herein, the term
perhalo-substituted group and related terms (such as, but not
limited to perhaloalkyl groups, perhaloalkenyl groups,
perhaloalkynyl groups, perhaloaryl groups and perhalo-heteroaryl
groups) means a group in which all of the available hydrogen groups
thereof are substituted with a halo group. For example,
perhalomethyl is --CX.sub.3; perhalophenyl is --C.sub.6X.sub.5,
where X represents one or more halo groups, such as, but not
limited to F.
[0045] The intermediate compounds of the present invention include
groups and sub-groups that can in each case be independently
selected from hydrocarbyl and/or substituted hydrocarbyl. As used
herein the term "hydrocarbyl" and similar terms, such as
"hydrocarbyl substituent," means: linear or branched
C.sub.1-C.sub.25 alkyl (e.g., linear or branched C.sub.1-C.sub.10
alkyl); linear or branched C.sub.2-C.sub.25 alkenyl (e.g., linear
or branched C.sub.2-C.sub.10 alkenyl); linear or branched
C.sub.2-C.sub.25 alkynyl (e.g., linear or branched C.sub.2-C.sub.10
alkynyl); C.sub.3-C.sub.12 cycloalkyl (e.g., C.sub.3-C.sub.10
cycloalkyl); C.sub.3-C.sub.12 heterocycloalkyl (having at least one
hetero atom in the cyclic ring); C.sub.5-C.sub.18 aryl (including
polycyclic aryl groups) (e.g., C.sub.5-C.sub.10 aryl);
C.sub.5-C.sub.18 heteroaryl (having at least one hetero atom in the
aromatic ring); and C.sub.6-C.sub.24 aralkyl (e.g.,
C.sub.6-C.sub.10 aralkyl).
[0046] Representative alkyl groups include but are not limited to
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and
decyl. Representative alkenyl groups include but are not limited to
vinyl, allyl and propenyl. Representative alkynyl groups include
but are not limited to ethynyl, 1-propynyl, 2-propynyl, 1-butynyl,
and 2-butynyl. Representative cycloalkyl groups include but are not
limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and
cyclooctyl substituents. Representative heterocycloalkyl groups
include but are not limited to imidazolyl, tetrahydrofuranyl,
tetrahydropyranyl and piperidinyl. Representative aryl groups
include but are not limited to phenyl, naphthyl, anthracynyl and
triptycenyl. Representative heteroaryl groups include but are not
limited to furanyl, pyranyl, pyridinyl, isoquinoline, and
pyrimidinyl. Representative aralkyl groups include but are not
limited to benzyl, and phenethyl.
[0047] The term "substituted hydrocarbyl" as used herein means a
hydrocarbyl group in which at least one hydrogen thereof has been
substituted with a group that is other than hydrogen, such as, but
not limited to, halo groups, hydroxyl groups, ether groups, thiol
groups, thio ether groups, carboxylic acid groups, carboxylic acid
ester groups, phosphoric acid groups, phosphoric acid ester groups,
sulfonic acid groups, sulfonic acid ester groups, nitro groups,
cyano groups, hydrocarbyl groups (e.g., alkyl, alkenyl, alkynyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and aralkyl
groups), and amine groups, such as --N(R.sub.11')(R.sub.12') where
R.sub.11' and R.sub.12' are each independently selected from
hydrogen, hydrocarbyl and substituted hydrocarbyl.
[0048] The term "substituted hydrocarbyl" is inclusive of
halohydrocarbyl (or halo substituted hydrocarbyl) substituents. The
term "halohydrocarbyl" as used herein, and similar terms, such as
halo substituted hydrocarbyl, means that at least one hydrogen atom
of the hydrocarbyl (e.g., of the alkyl, alkenyl, alkynyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and aralkyl groups)
is replaced with a halogen atom selected from chlorine, bromine,
fluorine and iodine. The degree of halogenation can range from at
least one hydrogen atom but less than all hydrogen atoms being
replaced by a halogen atom (e.g., a fluoromethyl group), to full
halogenation (perhalogenation) in which all replaceable hydrogen
atoms on the hydrocarbyl group have each been replaced by a halogen
atom (e.g., trifluoromethyl or perfluoromethyl). Correspondingly,
the term "perhalohydrocarbyl group" as used herein means a
hydrocarbyl group in which all replaceable hydrogens have been
replaced with a halogen. Examples of perhalohydrocarbyl groups
include, but are not limited to, perhalogenated phenyl groups and
perhalogenated alkyl groups.
[0049] The hydrocarbyl and substituted hydrocarbyl groups from
which the various groups described herein can each be independently
selected, in some instances and with some embodiments, can in each
case be independently and optionally interrupted with at least one
of --O--, --S--, --C(O)--, --C(O)O--, --S(O)--, --SO.sub.2--,
--N.dbd.N--, --N(R.sub.11')-- where R.sub.11' is selected from
hydrogen, hydrocarbyl or substituted hydrocarbyl,
--Si(OR.sub.8').sub.w(R.sub.8').sub.t--, where w and t are each
independently selected from 0 to 2, provided that the sum of w and
t is 2, and each R.sub.8' is independently selected from hydrogen,
hydrocarbyl and substituted hydrocarbyl, and combinations of two or
more thereof. As used herein, by interrupted with at least one of
--O--, --S--, --C(O)--, --C(O)O--, --OC(O)O--, --S(O)--,
--SO.sub.2--, --N.dbd.N--, --N(R.sub.11')--, and
--Si(OR.sub.8).sub.w(R.sub.8).sub.t--, means that at least one
carbon of, but less than all of the carbons of, the hydrocarbyl
group or substituted hydrocarbyl group, is in each case
independently replaced with one of the recited divalent non-carbon
linking groups. The hydrocarbyl and substituted hydrocarbyl groups
can be interrupted with two or more of the above recited linking
groups, which can be adjacent to each other or separated by one or
more carbons. For purposes of non-limiting illustration, a
combination of adjacent --C(O)-- and --N(R.sub.11')-- can provide a
divalent amide linking or interrupting group,
--C(O)--N(R.sub.11')--. For purposes of further non-limiting
illustration, a combination of adjacent --N(R.sub.11')--, --C(O)--
and --O-- can provide a divalent carbamate (or urethane) linking or
interrupting group, --N(R.sub.11')--C(O)--O--, where R.sub.11' is
hydrogen.
[0050] The term "alkyl" as used herein, in accordance with some
embodiments, means linear or branched alkyl, such as but not
limited to, linear or branched C.sub.1-C.sub.25 alkyl, or linear or
branched C.sub.1-C.sub.10 alkyl, or linear or branched
C.sub.2-C.sub.10 alkyl. Examples of alkyl groups from which the
various alkyl groups of the present invention can be selected from,
include, but are not limited to, those recited previously herein.
Alkyl groups of the various compounds of the present invention can,
with some embodiments, include one or more unsaturated linkages
selected from --CH.dbd.CH-- groups and/or one or more --C.ident.C--
groups, provided the alkyl group is free of two or more conjugated
unsaturated linkages. With some embodiments, the alkyl groups are
free of unsaturated linkages, such as --CH.dbd.CH-- groups and
--C.ident.C-- groups.
[0051] The term "cycloalkl" as used herein, in accordance with some
embodiments, means groups that are appropriately cyclic, such as
but not limited to, C.sub.3-C.sub.12 cycloalkyl (including, but not
limited to, cyclic C.sub.5-C.sub.7 alkyl) groups. Examples of
cycloalkyl groups include, but are not limited to, those recited
previously herein. The term "cycloalkyl" as used herein in
accordance with some embodiments also includes: bridged ring
polycycloalkyl groups (or bridged ring polycyclic alkyl groups),
such as but not limited to, bicyclo[2.2.1]heptyl (or norbornyl) and
bicyclo[2.2.2]octyl; and fused ring polycycloalkyl groups (or fused
ring polycyclic alkyl groups), such as, but not limited to,
octahydro-1H-indenyl, and decahydronaphthalenyl.
[0052] The term "heterocycloalkyl" as used herein, in accordance
with some embodiments, means groups that are appropriately cyclic,
such as but not limited to, C.sub.3-C.sub.12 heterocycloalkyl
groups or C.sub.5-C.sub.7 heterocycloalkyl groups, and which have
at least one hetero atom in the cyclic ring, such as, but not
limited to, O, S, N, P, and combinations thereof. Examples of
heterocycloalkyl groups include, but are not limited to, those
recited previously herein. The term "heterocycloalkyl" as used
herein, in accordance with some embodiments, also includes: bridged
ring polycyclic heterocycloalkyl groups, such as but not limited
to, 7-oxabicyclo[2.2.1]heptanyl; and fused ring polycyclic
heterocycloalkyl groups, such as but not limited to,
octahydrocyclopenta[b]pyranyl, and octahydro-1H-isochromenyl.
[0053] The term "heteroaryl," as used herein, in accordance with
some embodiments, includes but is not limited to C.sub.5-C.sub.18
heteroaryl, such as but not limited to C.sub.5-C.sub.10 heteroaryl
(including fused ring polycyclic heteroaryl groups) and means an
aryl group having at least one hetero atom in the aromatic ring, or
in at least one aromatic ring in the case of a fused ring
polycyclic heteroaryl group. Examples of heteroaryl groups include,
but are not limited to, those recited previously herein.
[0054] As used herein, the term "fused ring polycyclic-aryl-alkyl
group" and similar terms such as, fused ring polycyclic-alkyl-aryl
group, fused ring polycyclo-aryl-alkyl group, and fused ring
polycyclo-alkyl-aryl group means a fused ring polycyclic group that
includes at least one aryl ring and at least one cycloalkyl ring
that are fused together to form a fused ring structure. For
purposes of non-limiting illustration, examples of fused ring
polycyclic-aryl-alkyl groups include, but are not limited to
indenyl, 9H-flourenyl, cyclopentanaphthenyl, and indacenyl.
[0055] The term "aralkyl," as used herein, and in accordance with
some embodiments, includes but is not limited to C.sub.6-C.sub.24
aralkyl, such as but not limited to C.sub.6-C.sub.10 aralkyl, and
means an aryl group substituted with an alkyl group. Examples of
aralkyl groups include, but are not limited to, those recited
previously herein.
[0056] The intermediate compounds according to the present
invention, such as, but not limited to those represented by
Formulas (I-A) and (I-B), and the various groups thereof are
described in further detail herein as follows.
[0057] With some alternative embodiments, Z.sub.2 of Formula (I-A)
defines an optionally substituted fused ring. As used herein, the
term "Z.sub.2 defines an optionally substituted fused ring," means
that Z.sub.2 defines an optionally substituted fused ring that is
bonded to both Z.sub.1 and Z.sub.3. In accordance with some further
embodiments, the term "Z.sub.2 defines an optionally substituted
fused ring," does not include spiro compounds. For purposes of
non-limiting illustration, and in accordance with some embodiments,
when Z.sub.2 defines an optionally substituted fused ring, the
intermediate compound represented by Formula (I-A) is represented
by the following Formula (I-A'),
##STR00005##
[0058] With reference to Formula (I-A'): Ring-Z.sub.2 is selected
from cyclocalkyl, heterocycloalkyl, aryl, and heteroaryl; v is
selected from 1 to 8; and R.sub.21 for each v is independently
selected from hydrogen, cyano, nitro, halogen (such as, F, Cl, Br,
and I), hydrocarbyl, substituted hydrocarbyl, and
perhalohydrocarbyl. With some embodiments, Ring-Z.sub.2 is selected
from C.sub.6-cycloalkyl (having 6 carbon atoms in the cycloalkyl
ring) and C.sub.6-aryl (having 6 carbon atoms in the aryl
ring).
[0059] With reference to the intermediate compound represented by
Formula (I-A), Ring-A is selected from aryl.
[0060] With some embodiments, R.sup.1 for the intermediate compound
represented by Formula (I-A), for each n, is independently selected
from, hydrogen, halogen selected from bromo, iodo, fluoro and
chloro; C.sub.1-C.sub.20 linear or branched alkyl; C.sub.3-C.sub.10
cycloalkyl; and substituted or unsubstituted phenyl, in which the
phenyl substituents being selected from halogen,
halo(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy.
[0061] With some further embodiments, R.sup.1 of Formula (I-A), for
each n, is independently selected from, --O--R.sub.10' or
--S--R.sub.10', wherein each R.sub.10' independently is hydrogen,
C.sub.1-C.sub.20 alkyl, phenyl(C.sub.1-C.sub.20)alkyl,
mono(C.sub.1-C.sub.20)alkyl substituted
phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkoxy
substituted phenyl(C.sub.1-C.sub.20)alkyl,
(C.sub.1-C.sub.20)alkoxy(C.sub.2-C.sub.20)alkyl, C.sub.3-C.sub.10
cycloalkyl, or mono(C.sub.1-C.sub.20)alkyl substituted
C.sub.3-C.sub.10 cycloalkyl.
[0062] With some additional embodiments, R.sup.1 of Formula (I-A),
for each n, is independently selected from, --N(R.sub.11')R.sub.12'
or --C(O)--N(R.sub.11')(R.sub.12'), wherein R.sub.11' and R.sub.12'
are each independently hydrogen, C.sub.1-C.sub.20 alkyl, phenyl,
naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,
benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl,
benzopyridyl, fluorenyl, C.sub.1-C.sub.20 alkylaryl,
C.sub.3-C.sub.10 cycloalkyl, C.sub.4-C.sub.20 bicycloalkyl,
C.sub.5-C.sub.20 tricycloalkyl or C.sub.1-C.sub.20 alkoxyalkyl,
wherein the aryl group (of, for example, the C.sub.1-C.sub.20
alkoxyalkyl) is phenyl or naphthyl, or R.sub.11' and R.sub.12' come
together with the nitrogen atom to form a C.sub.3-C.sub.20
hetero-bicycloalkyl ring or a C.sub.4-C.sub.20 hetero-tricycloalkyl
ring.
[0063] With some additional further embodiments, R.sup.1 of Formula
(I-A), for each n, is independently selected from, a nitrogen
containing ring represented by the following graphic formula
XIIA,
##STR00006##
With reference to Formula (XIIA), each --Y-- is independently
chosen for each occurrence from --CH.sub.2-, --CH(R.sub.13')--,
--C(R.sub.13').sub.2--, --CH(aryl)-, --C(aryl).sub.2-, and
--C(R.sub.13')(aryl)-, and Z is --Y--, --O--, --S--, --NH--,
--N(R.sub.13')--, or --N(aryl)-, wherein each R.sub.13' is
independently C.sub.1-C.sub.20 alkyl, each aryl is independently
phenyl or naphthyl, m is an integer 1, 2 or 3, and p is an integer
0, 1, 2, or 3 and provided that when p is 0, Z is --Y--.
[0064] With some further additional embodiments, R.sup.1 of Formula
(I-A), for each n, is independently selected from, a group
represented by one of the following graphic formulas XIIB or
XIIC,
##STR00007##
With reference to Formulas (XIIB) and (XIIC), R.sub.15, R.sub.16,
and R.sub.17 are each independently hydrogen, C.sub.1-C.sub.20
alkyl, phenyl, or naphthyl, or the groups R.sub.15 and R.sub.16
together form a ring of 5 to 8 carbon atoms and each R.sup.d is
independently for each occurrence selected from C.sub.1-C.sub.20
alkyl, C.sub.1-C.sub.20 alkoxy, fluoro or chloro, and Q is an
integer 0, 1, 2, or 3.
[0065] The R.sup.1 group of Formula (I-A), for each n, is
independently selected from, with some embodiments, unsubstituted,
mono-, or di-substituted C.sub.4-C.sub.18 spirobicyclic amine, or
unsubstituted, mono-, and di-substituted C.sub.4-C.sub.18
spirotricyclic amine, wherein said substituents are independently
aryl, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, or
phenyl(C.sub.1-C.sub.20)alkyl.
[0066] In accordance with some alternative embodiments, two
adjacent R.sup.1 groups together form a group represented by one of
XIID and XIIE:
##STR00008##
With reference to Formula XIID and XIIE, T and T' are each
independently oxygen or the group --NR.sub.11'--, where R.sub.11',
R.sub.15, and R.sub.16 are as set forth above.
[0067] In accordance with some embodiments, R.sup.2 and R.sup.3 of
Formula (I-A) are each independently selected from: hydrogen;
halogen selected from F, Cl, Br, and I; C.sub.1-C.sub.20 linear or
branched alkyl; C.sub.3-C.sub.10 cycloalkyl; and substituted or
unsubstituted phenyl, the phenyl substituents being selected from
hydroxyl, halogen, carbonyl, C.sub.1-C.sub.20 alkoxycarbonyl,
cyano, halo(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy.
[0068] In accordance with some further embodiments, R.sup.2 and
R.sup.3 of Formula (I-A) are each independently selected from,
--C(O)N(R.sub.14)(R.sub.15) or --N(R.sub.14)(R.sub.15), where
R.sub.14 and R.sub.15 are each independently selected from:
hydrogen; C.sub.1-C.sub.20 linear or branched alkyl;
C.sub.3-C.sub.10 cycloalkyl; and substituted or unsubstituted
phenyl, the phenyl substituents being selected from halogen,
halo(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy, or R.sub.14 and R.sub.15 together form a
ring.
[0069] In accordance with some additional embodiments, R.sup.2 and
R.sup.3 of Formula (I-A) are each independently selected from,
--OR.sub.16 or --SR.sub.16, where each R.sub.16 is independently
selected from: C.sub.1-C.sub.20 linear or branched alkyl;
C.sub.3-C.sub.10 cycloalkyl; and substituted or unsubstituted
phenyl, the phenyl substituents being selected from halogen,
halo(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy.
[0070] In accordance with some embodiments, R.sup.4 and R.sup.5 of
Formula (I-A) are each independently selected from: (i) hydrogen,
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 haloalkyl,
C.sub.3-C.sub.10 cycloalkyl, allyl, benzyl, or mono-substituted
benzyl, said benzyl substituents being chosen from halogen,
C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 alkoxy; (ii) an
unsubstituted, mono- di- or tri-substituted group chosen from
phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl,
benzofuranyl, thienyl, benzothienyl, dibenzofuranyl,
dibenzothienyl, carbazolyl, or indolyl, said group substituents in
each case being independently chosen from halogen, C.sub.1-C.sub.20
alkyl or C.sub.1-C.sub.20 alkoxy; (iii) mono-substituted phenyl,
said substituent located at the para position being
--(CH.sub.2).sub.t-- or --O--(CH.sub.2).sub.t--, wherein t is the
integer 1, 2, 3, 4, 5 or 6, said substituent being connected to an
aryl group which is a member of a photochromic material; and (iv)
the group --CH(R.sup.10)G, wherein R.sup.10 is hydrogen,
C.sub.1-C.sub.6 alkyl or the unsubstituted, mono- or di-substituted
aryl groups phenyl or naphthyl, and G is --CH.sub.2OR.sup.11,
wherein R.sup.11 is hydrogen, C.sub.1-C.sub.20 alkyl,
C.sub.1-C.sub.20 alkoxy(C.sub.1-C.sub.20)alkyl,
phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkoxy
substituted phenyl(C.sub.1-C.sub.20)alkyl, or the unsubstituted,
mono- or di-substituted aryl groups phenyl or naphthyl, each of
said phenyl and naphthyl group substituents being C.sub.1-C.sub.20
alkyl or C.sub.1-C.sub.20 alkoxy; or (v) R.sup.4 and R.sup.5
together form a spiro substituent selected from a substituted or
unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon
atoms, a substituted or unsubstituted spiro-heterocyclic ring
containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including
the spirocarbon atom, said spiro-carbocyclic ring and
spiro-heterocyclic ring being annellated with 0, 1 or 2 benzene
rings, said substituents being hydrogen or C.sub.1-C.sub.20
alkyl.
[0071] With further reference to Formula (I-A) and with some
embodiments, R.sup.6 for Formula (I-A) is selected from hydrogen,
--C(O)--R.sub.19 and --S(O)(O)R.sub.19, wherein R.sub.19 is
selected from C.sub.1-C.sub.20 linear or branched alkyl and
C.sub.1-C.sub.20 linear or branched perfluoroalkyl.
[0072] Ring-A for Formula (I-A), in accordance with some
embodiments, is C.sub.6-aryl.
[0073] With some embodiments, R.sup.1 for Formula (I-A) for each n
is independently selected from hydrogen, C.sub.1-C.sub.6 linear or
branched alkyl, C.sub.3-C.sub.7 cycloalkyl, C.sub.1-C.sub.8
haloalkyl, fluoro, chloro, bromo, iodo, and --O--R.sub.10'.
[0074] With some embodiments, R.sup.2 and R.sup.3 for Formula (I-A)
are each independently selected from: hydrogen; C.sub.1-C.sub.6
linear or branched alkyl; C.sub.3-C.sub.7 cycloalkyl; and
substituted or unsubstituted phenyl, the phenyl substituents being
selected from halogen, halo(C.sub.1-C.sub.6)alkyl, C.sub.1-C.sub.6
alkyl or C.sub.1-C.sub.6 alkoxy.
[0075] With some embodiments, R.sup.4 and R.sup.5 for Formula (I-A)
are each independently selected from hydrogen, C.sub.1-C.sub.8
alkyl, C.sub.1-C.sub.8 haloalkyl, and C.sub.3-C.sub.7 cycloalkyl,
or R.sup.6 and R.sup.7 together form a spiro substituent selected
from a substituted or unsubstituted spiro-carbocyclic ring
containing 3 to 6 carbon atoms.
[0076] With further reference to Formula (I-A) and with some
embodiments, R.sup.6 for Formula (I-A) is selected from
--C(O)--R.sub.19 and --S(O)(O)R.sub.19, wherein R.sub.19 is
selected from C.sub.1-C.sub.10 linear or branched alkyl and
C.sub.1-C.sub.10 linear or branched perfluoroalkyl.
[0077] With reference to the intermediate compound represented by
Formula (I-A), and in accordance with some embodiments, Z.sub.2 is
N--R.sub.13, and R.sub.13 is a group L represented by the following
Formula (II), and optionally at least one R.sup.1 independently for
each n, is selected from the group L represented by the following
Formula (II),
--[S.sub.1].sub.c-[Q.sub.1-[S.sub.2].sub.d].sub.d'-[Q.sub.2-[S.sub.3].su-
b.e].sub.e'-[Q.sub.3-[S.sub.4].sub.f].sub.f'--S.sub.5--P Formula
(II)
[0078] With reference to Formula (II), and in accordance with some
embodiments, (a) Q.sub.1, Q.sub.2, and Q.sub.3 for each occurrence,
are independently selected from a divalent group selected from
optionally substituted aryl, optionally substituted heteroaryl,
optionally substituted cycloalkyl, and optionally substituted
heterocycloalkyl. The aryl substituents, heteroaryl substituents,
cycloalkyl substituents, and heterocycloalkyl substituents are,
with some embodiments, each independently selected from P (as
described in further detail below), liquid crystal mesogens,
halogen, poly(C.sub.1-C.sub.18 alkoxy), C.sub.1-C.sub.18
alkoxycarbonyl, C.sub.1-C.sub.18 alkylcarbonyl, C.sub.1-C.sub.18
alkoxycarbonyloxy, aryloxycarbonyloxy,
perfluoro(C.sub.1-C.sub.18)alkoxy,
perfluoro(C.sub.1-C.sub.18)alkoxycarbonyl,
perfluoro(C.sub.1-C.sub.18)alkylcarbonyl,
perfluoro(C.sub.1-C.sub.18)alkylamino,
di-(perfluoro(C.sub.1-C.sub.18)alkyl)amino,
perfluoro(C.sub.1-C.sub.18)alkylthio, C.sub.1-C.sub.18 alkylthio,
C.sub.1-C.sub.18 acetyl, C.sub.3-C.sub.10 cycloalkyl,
C.sub.3-C.sub.10 cycloalkoxy, straight-chain C.sub.1-C.sub.18
alkyl, and branched C.sub.1-C.sub.18 alkyl. The straight-chain
C.sub.1-C.sub.18 alkyl and branched C.sub.1-C.sub.18 alkyl, with
some embodiments, are mono-substituted with a group selected from
cyano, halogen, and C.sub.1-C.sub.18 alkoxy. Alternatively, and
with some embodiments, the straight-chain C.sub.1-C.sub.18 alkyl
and branched C.sub.1-C.sub.18 alkyl are poly-substituted with at
least two groups independently selected from halogen,
-M(T).sub.(v-1) and -M(OT).sub.(v-1), in which M is chosen from
aluminum, antimony, tantalum, titanium, zirconium and silicon, T is
chosen from organofunctional radicals, organofunctional hydrocarbon
radicals, aliphatic hydrocarbon radicals and aromatic hydrocarbon
radicals, and v is the valence of M.
[0079] With further reference to Formula (II), and in accordance
with some further embodiments, (b) c, d, e, and f are each
independently chosen from an integer of 1 to 20; and each S.sub.1,
S.sub.2, S.sub.3, S.sub.4, and S.sub.5 is independently chosen for
each occurrence from a spacer unit selected from (i), (ii), and
(iii) as described as follows. With some embodiments, each S.sub.1,
S.sub.2, S.sub.3, S.sub.4, and S.sub.5 is independently chosen for
each occurrence from a spacer unit selected from (i) optionally
substituted alkylene, optionally substituted haloalkylene,
--Si(CH.sub.2).sub.g--, and --(Si[(CH.sub.3).sub.2]O).sub.h--,
wherein g for each occurrence is independently chosen from an
integer from 1 to 20; h for each occurrence is independently chosen
from an integer from 1 to 16; and said substitutes for the alkylene
and haloalkylene are independently selected from C.sub.1-C.sub.18
alkyl, C.sub.3-C.sub.10 cycloalkyl and aryl. With some further
embodiments, each S.sub.1, S.sub.2, S.sub.3, S.sub.4, and S.sub.5
is independently chosen for each occurrence from a spacer unit
selected from (ii) --N(Z)--, --C(Z).dbd.C(Z)--, --C(Z).dbd.N--,
--C(Z').sub.2--C(Z').sub.2--, and a single bond, wherein Z for each
occurrence is independently selected from hydrogen,
C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.10 cycloalkyl and aryl, and
Z' for each occurrence is independently selected from
C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.10 cycloalkyl and aryl. With
some additional embodiments, each S.sub.1, S.sub.2, S.sub.3,
S.sub.4, and S.sub.5 is independently chosen for each occurrence
from a spacer unit selected from (iii) --O--, --C(.dbd.O)--,
--C.ident.C--, --N.dbd.N--, --S--, --S(.dbd.O)--,
--(O.dbd.)S(.dbd.O)--, --(O.dbd.)S(.dbd.O)O--,
--O(O.dbd.)S(.dbd.O)O-- and straight-chain or branched
C.sub.1-C.sub.24 alkylene residue, said C.sub.1-C.sub.24 alkylene
residue being unsubstituted, mono-substituted by cyano or halogen,
or poly-substituted by halogen. With further reference to each of
S.sub.1, S.sub.2, S.sub.3, S.sub.4, and S.sub.5, and with some
embodiments, there is the proviso that when two spacer units
comprising heteroatoms are linked together the spacer units are
linked so that heteroatoms are not directly linked to each other.
There is a further proviso, with some embodiments, that each bond
between S.sub.1 and the nitrogen atom of N--R.sub.13 of the
intermediate compound represented by Formula (I-A) is in each case
free of two heteroatoms linked together, and the bond between
S.sub.5 and P is free of two heteroatoms linked to each other.
[0080] With further reference to Formula (II), and in accordance
with some further embodiments, (c) P for each occurrence is
independently selected from hydroxy, amino, C.sub.2-C.sub.18
alkenyl, C.sub.2-C.sub.18 alkynyl, azido, silyl, siloxy,
silylhydride, (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato,
thioisocyanato, acryloyloxy, methacryloyloxy,
2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl,
aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylic
ester, acryloylamino, methacryloylamino, aminocarbonyl,
C.sub.1-C.sub.18 alkyl aminocarbonyl,
aminocarbonyl(C.sub.1-C.sub.18)alkyl, C.sub.1-C.sub.18
alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl,
hydroxy(C.sub.1-C.sub.18)alkyl, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.18 alkoxy, amino(C.sub.1-C.sub.18)alkyl,
C.sub.1-C.sub.18alkylamino, di-(C.sub.1-C.sub.18)alkylamino,
C.sub.1-C.sub.18 alkyl(C.sub.1-C.sub.18)alkoxy, C.sub.1-C.sub.18
alkoxy(C.sub.1-C.sub.18)alkoxy, nitro, poly(C.sub.1-C.sub.18)alkyl
ether,
(C.sub.1-C.sub.18)alkyl(C.sub.1-C.sub.18)alkoxy(C.sub.1-C.sub.18)alkyl,
polyethyleneoxy, polypropyleneoxy, ethylene, acryloyl,
acryloyloxy(C.sub.1-C.sub.18)alkyl, methacryloyl,
methacryloyloxy(C.sub.1-C.sub.18)alkyl, 2-chloroacryloyl,
2-phenylacryloyl, acryloyloxyphenyl, 2-chloroacryloylamino,
2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano,
isocyanato(C.sub.1-C.sub.18)alkyl, itaconic acid ester, vinyl
ether, vinyl ester, a styrene derivative, main-chain and side-chain
liquid crystal polymers, siloxane derivatives, ethyleneimine
derivatives, maleic acid derivatives, maleimide derivatives,
fumaric acid derivatives, unsubstituted cinnamic acid derivatives,
cinnamic acid derivatives that are substituted with at least one of
methyl, methoxy, cyano and halogen, and substituted or
unsubstituted chiral or non-chiral monovalent or divalent groups
chosen from steroid radicals, terpenoid radicals, alkaloid radicals
and mixtures thereof, wherein the substituents are independently
chosen from C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkoxy, amino,
C.sub.3-C.sub.10 cycloalkyl, C.sub.1-C.sub.18
alkyl(C.sub.1-C.sub.18)alkoxy, fluoro(C.sub.1-C.sub.18)alkyl,
cyano, cyano(C.sub.1-C.sub.18)alkyl, cyano(C.sub.1-C.sub.18)alkoxy
or mixtures thereof, or P is a structure having from 2 to 4
reactive groups, or P is an unsubstituted or substituted ring
opening metathesis polymerization precursor, or P is a substituted
or unsubstituted photochromic compound.
[0081] With additional reference to Formula (II), and in accordance
with some further embodiments, (d) d', e' and f' are each
independently chosen from 0, 1, 2, 3, and 4, provided that the sum
of d'+e'+f' is at least 1.
[0082] In accordance with some embodiments, for the group L
represented by Formula (II), (a) Q.sub.1, Q.sub.2, and Q.sub.3 for
each occurrence, are independently selected from optionally
substituted aryl and optionally substituted cycloalkyl.
[0083] With further reference to Formula (II), and in accordance
with some further embodiments, (b) each S.sub.1, S.sub.2, S.sub.3,
S.sub.4, and S.sub.5 of Formula (VII) is independently chosen for
each occurrence from a spacer unit selected from (ii) and (iii) as
described as follows. Each S.sub.1, S.sub.2, S.sub.3, S.sub.4, and
S.sub.5 of Formula (VII), with some embodiments, is independently
chosen for each occurrence from a spacer unit selected from (ii)
--N(Z)--, --C(Z).dbd.C(Z)--, --C(Z).dbd.N--,
--C(Z).sub.2--C(Z').sub.2--, and a single bond, wherein Z for each
occurrence is independently selected from hydrogen, C.sub.1-C.sub.8
alkyl, C.sub.3-C.sub.6 cycloalkyl and aryl, and Z' for each
occurrence is independently selected from C.sub.1-C.sub.8 alkyl,
C.sub.3-C.sub.6 cycloalkyl and aryl. Each S.sub.1, S.sub.2,
S.sub.3, S.sub.4, and S.sub.5 of Formula (VII), with some further
embodiments, is independently chosen for each occurrence from a
spacer unit selected from (iii) --O--, --C(.dbd.O)--,
--C.ident.C--, --N.dbd.N--, --S--, --S(.dbd.O)--, and
straight-chain or branched C.sub.1-C.sub.12 alkylene residue, said
C.sub.1-C.sub.12 alkylene residue being unsubstituted,
mono-substituted by cyano or halogen, or poly-substituted by
halogen.
[0084] In accordance with some additional embodiments, for the
group L represented by Formula (II), (c) P for each occurrence is
independently selected from hydrogen, hydroxy, amino,
C.sub.2-C.sub.8 alkenyl, C.sub.2-C.sub.8 alkynyl, acryloyloxy,
methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl,
2-(methacryloyloxy)ethylcarbamyl, epoxy, carboxylic acid,
carboxylic ester, acryloylamino, methacryloylamino, aminocarbonyl,
C.sub.1-C.sub.8 alkyl aminocarbonyl,
aminocarbonyl(C.sub.1-C.sub.8)alkyl, C.sub.1-C.sub.8
alkyloxycarbonyloxy, halocarbonyl, aryl,
hydroxy(C.sub.1-C.sub.8)alkyl, C.sub.1-C.sub.8 alkyl,
C.sub.1-C.sub.8 alkoxy, amino(C.sub.1-C.sub.8)alkyl,
C.sub.1-C.sub.8 alkylamino, di-(C.sub.1-C.sub.8)alkylamino,
C.sub.1-C.sub.8 alkyl(C.sub.1-C.sub.8)alkoxy, C.sub.1-C.sub.8
alkoxy(C.sub.1-C.sub.8)alkoxy, nitro, poly(C.sub.1-C.sub.8)alkyl
ether,
(C.sub.1-C.sub.8)alkyl(C.sub.1-C.sub.8)alkoxy(C.sub.1-C.sub.8)alkyl,
polyethyleneoxy, polypropyleneoxy, ethylene, acryloyl,
acryloyloxy(C.sub.1-C.sub.18)alkyl, methacryloyl,
methacryloyloxy(C.sub.1-C.sub.8)alkyl, 2-chloroacryloyl,
2-phenylacryloyl, acryloyloxyphenyl, 2-chloroacryloylamino,
2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano,
isocyanato(C.sub.1-C.sub.18)alkyl, itaconic acid ester, vinyl
ether, and vinyl ester.
[0085] In accordance with some further additional embodiments, for
the group L represented by Formula (II), (b) each S.sub.1, S.sub.2,
S.sub.3, S.sub.4, and S.sub.5 is independently chosen for each
occurrence from a spacer unit selected from: (ii) --N(Z)--,
--C(Z).dbd.C(Z)--, and a single bond, wherein Z for each occurrence
is independently selected from hydrogen, C.sub.1-C.sub.8 alkyl,
C.sub.3-C.sub.6 cycloalkyl and aryl; and (iii) --O--,
--O(.dbd.O)--, --C.ident.C--, and straight-chain or branched
C.sub.1-C.sub.6 alkylene residue, said C.sub.1-C.sub.6 alkylene
residue being unsubstituted, mono-substituted by cyano or halogen,
or poly-substituted by halogen.
[0086] In accordance with some additional further embodiments, for
the group L represented by Formula (II), (c) P for each occurrence
is independently selected from hydrogen, hydroxy, amino,
C.sub.2-C.sub.8 alkenyl, C.sub.2-C.sub.8 alkynyl, and aryl.
[0087] In accordance with some embodiments of the present
invention, each group L as represented by Formula (II) is
independently selected from the following non-limiting groups:
##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013##
##STR00014## ##STR00015## ##STR00016##
[0088] With regard to the above non-limiting examples of L groups,
there is the proviso that that R.sub.13 of N--R.sub.13 is only
selected from L(5), L(6), L(7), L(8), L(9), L(12), L(14), L(21),
L(24), L(27), L(34), L(36), L(h), L(i), L(j), L(l), L(m), L(n),
L(n), L(o), L(p), L(u), L(v), L(w), L(ac), L(ae), L(af), L-DC-(a),
L-DC-(b), L-DC-(c), L-DC-(d), L-DC-(e), L-DC-(h), L-DC-(i), and
L-DC-(l).
[0089] In accordance with some embodiments, the intermediate
compound represented by Formula (I-A), after formation thereof, can
be subjected to one or more additional chemical reactions for
purposes of modifying R.sub.13 (when group Z.sub.2 is N--R.sub.13),
such that R.sub.13 is, or is converted to, an L group (or group L)
as described previously herein with reference to Formula (II).
Examples of additional chemical reactions that the intermediate
compound represented by Formula (I-A) can be subjected to include,
but are not limited to, palladium-catalyzed cross couplings,
etherifications, esterifications, amidations, and
condensations.
[0090] In accordance with some embodiments of the present
invention, Z.sub.1 and Z.sub.3 of Formula (I-A) are each C(O).
[0091] The intermediate compound represented by Formula (I-A), with
some embodiments, is represented by the following Formula (I-B), in
which Ring-A is an R.sup.1 substituted C.sub.6-aryl (or phenyl)
group:
##STR00017##
With reference to Formula (I-B), n is 1 to 4. With further
reference to Formula (I-B), R.sup.1, R.sup.2-R.sup.6, and
Z.sub.1-Z.sub.3 are each as described herein with reference to
Formula (I-A). The ring including Z.sub.1-Z.sub.3 is bonded to the
ring positions of the indo portion of the intermediate compound as
shown in Formula (I-B).
[0092] Examples of intermediate compounds according to the present
invention, based on Formula (I-B), include, but are not limited to,
the following:
##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022##
##STR00023##
[0093] The intermediate compounds of the present invention are
prepared, with some embodiments, by reacting together a dienophile
and a lactone compound that includes a diene, in the presence of a
catalyst (as will be described in further detail herein), and a
carboxylic acid anhydride, when R.sub.6 of Formula (I-A) is
--C(O)--R.sub.19. Such non-limiting methods of preparing the
intermediate compounds of the present invention are shown in
Examples 1-5 of the Examples further herein. For purposes of
non-limiting illustration, the intermediate compounds of the
present invention, such as represented by Formula (I-A) can be
prepared in accordance with the general Scheme-(1) of FIG. 1. With
reference to Scheme-1 of FIG. 1, the intermediate compound
represented by Formula (I-A), is prepared, with some embodiments,
by reaction of a diene represented by the following Formula (II-A)
with a lactone compound represented by the following Formula
(III-A) in the presence of a catalyst, and a carboxylic acid
anhydride represented by the following Formula (IV):
##STR00024##
[0094] With reference to the above Formulas (II-A), (III-A), and
(IV), Z.sub.1, Z.sub.2, Z.sub.3, R.sup.1-R.sup.5, and R.sub.19 are
each as described herein with reference to Formula (I-A). The wavy
bonds () of Formula (III-A) indicate that the positions of the
Ring-(A) and the five member ring (including Y, R.sup.2 and
R.sup.3) can be switched relative to the double bond extending from
the junction of the two wavy bonds, and as such, Formula (III-A)
represents both structural isomers relative to the double bond. For
purposes of further non-limiting illustration, the lactone compound
represented by Formula (III-A) includes lactone compounds
represented by the following Formula (III-A') and Formula
(III-A'').
##STR00025##
[0095] With reference to Scheme-(1) of FIG. 1, Y of the lactone
compound represented by Formula (III-A) is selected from O, S, and
N(R.sub.18), where R.sub.18 is selected from hydrogen, hydrocarbyl,
and substituted hydrocarbyl. While not intending to be bound by any
theory, it is believed that the dienophile represented by Formula
(II-A) and the cyclic diene moiety (that includes Y, R.sup.2 and
R.sup.3) of the lactone represented by Formula (III-A) react
together by a Diels-Alder reaction.
[0096] With further reference to Scheme-(1) of FIG. 1, the group Y
of the lactone compound, such as represented by Formula (III-A), is
not present in or otherwise incorporated into the structure of the
intermediate compound represented by Formula (I-A). With some
embodiments, during the course of the reaction represented by
Scheme-1 of FIG. 1, Y of the lactone compounds, such as represented
by Formula (III-A), forms: H.sub.2O (when Y is O); SH.sub.2 (when Y
is S); or NH.sub.2(R.sub.18) (when Y is N(R.sub.18)). While not
intending to be bound by any theory, the conversion of Y of the
lactone, such as represented by Formula (III-A), to H.sub.2O,
SH.sub.2, or NH.sub.2(R.sub.18) is believed to occur during an
aromatization step of the reaction.
[0097] As shown in Examples 6-10, the intermediate compounds of the
present invention are, with some embodiments, also prepared from
the intermediate compound represented by Formula (I-A) through
single-step or multi-step functional group transformation
procedures in accordance with art-recognized methods. Non-limiting
examples of transformation procedures include, but are not limited
to hydrolysis, Friedel-Crafts reactions, palladium-catalyzed cross
couplings, cyanation chemistries, etherifications, C--H bond
activation chemistries, borylation chemistries, esterifications,
amidations, condensations, oxidation chemistries and reduction
chemistries. Example 6-8 provide a non-limiting demonstration of
how a hydroxy substitution is obtained through hydrolysis. Example
9 provides a non-limiting demonstration of how a lengthening group
is attached via a Suzuki coupling reaction. Example 10 provides a
non-limiting demonstration of the use of condensation chemistry to
convert an anhydride functionality to an imide functionality.
[0098] While not intending to be bound by any theory and for
purposes of non-limiting illustration, and based on the evidence
presently at hand, the method by which the intermediate compounds
of the present invention are prepared, as represented by Scheme-1
of FIG. 1, and in accordance with some embodiments, is believed to
proceed more particularly by one or both of the pathways as
represented by the Scheme-(2) of FIG. 2 and/or Scheme-(3) of FIG. 3
of the drawings.
[0099] With reference to the pathway represented by Scheme-(2) of
FIG. 2, in step (a), the lactone isomer represented by Formula
(III-A'') is converted to Intermediate-(i) in the presence of a
catalyst, as will be described in further detail herein. In
Scheme-(2), the catalyst, the dienophile represented by Formula
(II-A), and the carboxylic acid anhydride represented by Formula
(IV) are together present with the lactone isomer represented by
Formula (III-A'') at the beginning of the reaction, but are
depicted as having a more prominent or direct role at different
steps throughout the reaction scheme. In step (b), Intermediate-(i)
and the dienophile represented by Formula (II-A) react together by
what is believed to be a Diels-Alder reaction so as to form
Intermediate-(ii). In step (c), which is an aromatization step,
Intermediate-(ii) and the carboxylic acid anhydride represented by
Formula (IV) together form Intermediate-(iii). During step (c),
there is the concurrent formation of YH.sub.2. In step (d)
Intermediate (iii) by intramolecular rearrangement is converted to
Intermediate (iv) with the loss of one molecule of H.sub.2O. In
step (e) Intermediate-(iv) and the carboxylic acid anhydride
represented by Formula (IV) together form the intermediate compound
represented by Formula (I-A).
[0100] With reference to the pathway represented by Scheme-(3) of
FIG. 3, in step (a) via a Diels-Alder reaction, the lactone isomer
represented by Formula (III-A'') is converted to Intermediate-(i')
in the presence of the dienophile represented by Formula (II-A) and
catalyst, as will be described in further detail herein. In
Scheme-(3), the catalyst, the dienophile represented by Formula
(II-A), and the carboxylic acid anhydride represented by Formula
(IV) are together present with the lactone isomer represented by
Formula (III-A') at the beginning of the reaction, but are depicted
as having a more prominent or direct role at different steps
throughout the reaction scheme. In step (b), which is an
aromatization step, Intermediate-(i') together with the carboxylic
acid anhydride represented by Formula (IV) is converted to
Intermediate-(iii). During the course of step (b) of Scheme-(3)
there is the concurrent formation of YH.sub.2. In step (c),
Intermediate (iii) by intramolecular rearrangement is converted to
Intermediate (iv) with the loss of one molecule of H.sub.2O. In
step (d), Intermediate-(iv) and the carboxylic acid anhydride
represented by Formula (IV) together form the intermediate compound
represented by Formula (I-A).
[0101] With further reference to Scheme-(3) of FIG. 3, and without
intending to be bound by any theory, it is believed that the
structural isomer of the lactone compound represented by Formula
(III-A') also participates, though indirectly, in the illustrated
reaction scheme by being converted to the structural isomer
represented by Formula (III-A''). For purposes of illustration, and
not intending to be bound by any theory, the lactone structural
isomers represented by Formulas (III-A') and (III-A'') are believed
to rearrange from one to the other as represented by Scheme-4 of
FIG. 4, in the presence of acid catalyst (which is not depicted in
Scheme-4 of FIG. 4).
[0102] With reference to Scheme-4 of FIG. 4, the lactone compound
represented by Formula (III-A') is in equilibrium with the
open-ringed ionic isomer represented by Formula (III-C1), which is
in equilibrium with the spiro-lactone isomer represented by Formula
(III-C), which is in equilibrium with the ring-opened ionic isomer
represented by Formula (III-C2), which is in equilibrium with the
lactone compound represented by Formula (III-A''). As such, by way
of the structural isomers represented by Formulas (III-C1),
(III-C), and (III-C2), the lactone structural isomers represented
by Formulas (III-A') and (III-A'') are converted from one to the
other. As the lactone structural isomer represented by Formula
(III-A'') is reacted/consumed in the reaction represented by
Scheme-3 of FIG. 3, the lactone structural isomer represented by
Formula (III-A') is converted to the structural isomer represented
by Formula (III-A'') as the effective equilibrium there-between is
correspondingly shifted to replace the structural isomer
represented by Formula (III-A'') as it is consumed in the reaction.
Similarly, as the lactone structural isomer represented by Formula
(III-A'') is reacted/consumed in the reaction represented by
Scheme-2 of FIG. 2, the lactone structural isomer represented by
Formula (III-A') is converted to the structural isomer represented
by Formula (III-A'') as the effective equilibrium there-between is
correspondingly shifted to replace the structural isomer
represented by Formula (III-A'') as it is consumed in the reaction
represented by Scheme-2 of FIG. 2.
[0103] In accordance with some embodiments, the intermediate
compounds of the present invention are prepared in the presence of
a catalyst that is selected from at least one Lewis acid
represented by the following Formula (V) and Formula (VI),
M.sup.y+(.sup.-O--SO.sub.2--R.sub.20).sub.y (V)
and
M.sup.y+(X.sup.-).sub.y (VI)
Independently for each of Formula (V) and Formula (VI), M
represents a metal, y is the valence of the metal, R.sub.20 for
each y is independently selected from hydrocarbyl and
halohydrocarbyl, and X for each y is independently selected from
halogen. More particularly, and with reference to the Lewis acid
represented by Formula (VI), X.sup.- for each y is independently a
halogen anion. More particularly, and independently for each of
Formula (V) and Formula (VI), M.sup.y+ represents a metal cation,
and y is the valence of the metal cation.
[0104] With some further embodiments: the metal M of Formula (V)
and Formula (VI) is in each case independently selected from Bi, B,
Al, Hf, Sc, Cu, Yb, Ti, Sn, Fe, Zn, Ag, Y, In, Nb and Mg; R.sub.20
of Formula (V) is selected from C.sub.1-C.sub.10 linear or branched
alkyl, and C.sub.1-C.sub.10 linear or branched perfluoroalkyl; and
X of Formula (VI) is selected from F, Cl, I, and Br.
[0105] In accordance with some additional embodiments, the catalyst
is selected from one or more Lewis acids represented by Formula
(V), in which M is Bi, y is 3, and R.sub.20 is selected from
C.sub.1-C.sub.10 linear or branched perfluoroalkyl, such as
trifluoromethane.
[0106] The catalyst, with some embodiments, is present in an amount
of at least 0.001 percent by moles, based on moles of the lactone
compound represented by Formula (III-A), such as from 0.001 to 99
percent by moles, or from 0.01 to 30 percent by moles, in each case
based on moles of the lactone compound represented by Formula
(III-A).
[0107] The lactone compounds that can be used to prepare the
intermediate compounds of the present invention, are prepared by
art-recognized procedures with some embodiments. For purposes of
non-limiting illustration, and with reference to Scheme-5 of FIG.
5, the lactone compound represented by Formula (III-A) is prepared,
in accordance with some embodiments, by reacting an acid ester
represented by Formula (1) with a metal hydride reducing agent that
is defined herein to include an organo metal hydride reducing
agent, or a nucleophile represented by at least one of Formula (2)
and/or Formula (3). The wavy bonds () of Formula (1) indicate that
the positions of the Ring-(A) and the five member ring (including
Y, R.sup.2 and R.sup.3) can be switched relative to the double bond
extending from the junction of the two wavy bonds, and as such,
Formula (1) represents both structural isomers relative to the
double bond.
[0108] With further reference to Scheme-5 of FIG. 5, the metal
hydride reducing agent is typically used when R.sup.4 and R.sup.5
are each hydrogen. The metal hydride reducing agent can, with some
embodiments, be selected from sodium borohydride and lithium
aluminum hydride, or an organo metal hydride reducing agent. The
organo metal hydride reducing agent can be one or more
di(C.sub.1-C.sub.20 alkyl) aluminum hydride reducing agents, such
as one or more di(C.sub.1-C.sub.6 alkyl) aluminum hydride reducing
agents, examples of which include, but are not limited to, diethyl
aluminum hydride and diisobutyl aluminum hydride.
[0109] With reference to Formulas (2) and (3) of Scheme-5 of FIG.
5, M.sup.1 and M.sup.2 are each independently selected from
Si(R.sup.31).sub.3, where each R.sup.31 is independently selected
from C.sub.1-C.sub.8 alkyl, or M.sup.1 and M.sup.2 each
independently represent a counterion that includes a metal selected
from Mg, Li, Mn, Cu, Zn, Al, Ti, Ln, and combinations thereof. With
some embodiments, R.sub.30 of the acid ester represented by Formula
(1) is selected from hydrocarbyl and substituted hydrocarbyl. With
some further embodiments, R.sub.30 of the acid ester represented by
Formula (1) is selected from linear or branched C.sub.1-C.sub.20
alkyl, such as linear or branched C.sub.1-C.sub.6 alkyl (such as
ethyl, with some embodiments).
[0110] According to some embodiments, and with further reference to
Scheme-5 of FIG. 5, M.sup.1 and M.sup.2 of Formulas (2) and (3)
also include a halogen, and can be represented by (M.sup.1X).sup.+
and (M.sup.2X).sup.+, in which X is a halogen. Each of M.sup.1 and
M.sup.2 of Formulas (2) and (3) can each be selected from
(MgX).sup.+, in which X is selected from halogen, such as Cl, Br
and I, examples of which include, but are not limited to,
(MgCl).sup.+, (MgBr).sup.+ and (MgI).sup.+.
[0111] With some embodiments, the nucleophiles represented by
Formulas (2) and (3) of Scheme-5 of FIG. 5, are each Grignard
reagents, and the reaction represented by Scheme-5 is a Grignard
reaction, which is conducted under Grignard reaction conditions.
The reaction represented by Scheme-5 is typically conducted in the
presence of an appropriate solvent, such as tetrahydrofuran (THF),
and under conditions of ambient pressure (e.g., approximately 1
atm), under an inert atmosphere (e.g., under a nitrogen sweep),
such as from -30.degree. C. to 60.degree. C., or from -20.degree.
C. to 45.degree. C., or from -10.degree. C. to 30.degree. C., and
optionally with reflux.
[0112] The reaction of the acid ester represented by Formula (1)
with the nucleophile represented by Formulas (2) and/or (3), of
Scheme-5, is with some embodiments, conducted in the presence of
metal salts. Examples of metal salts that can be present include,
but are not limited to, aluminum chloride (AlCl.sub.3), tin
chloride, zinc chloride, bismuth triflate, alkali metal halides,
anhydrous alkaline metal halides, rate earth metal salts, e.g.,
lanthanide halides, such as lanthanum III chloride, and lanthanide
triflate, and combinations thereof. Examples of alkali metal
halides that can be present include, but are not limited to, sodium
halides and/or potassium halides, such as sodium chloride (NaCl)
and/or potassium chloride (KCl). Examples of alkaline metal halides
that can be present include, but are not limited to, anhydrous
calcium halides, anhydrous lithium halides and/or anhydrous
magnesium halides, such as calcium chloride, lithium chloride and
magnesium chloride. The metal salt is typically present in an
amount of from 0.1 molar percent to 600 molar percent, or from 1.0
to 100 molar percent, or from 10 to 50 molar percent, based on 100
molar percent of the starting materials. The molar percent is
defined herein as the percentage of the number of moles of the
metal salt per liter of solute based on the total moles per liter
of solute of the acid ester represented by Formula (1) and the
nucleophiles represented by Formulas (2) and (3) in Scheme-5.
[0113] In accordance with some embodiments, the lactone compounds
represented by Formula (III-A) (including Formulas (III-A') and
(III-A'')), after formation thereof, can be subjected to one or
more additional chemical reactions for purposes of modifying one or
more of the groups thereof, such as the R.sup.1, R.sup.4, R.sup.5,
R.sup.6, and/or R.sup.7 groups. Examples of modified groups
include, but are not limited to, lengthening groups, such as group
L (or L groups) as described previously herein with reference to
Formula (II). With some embodiments, the groups of the lactone
compounds represented by Formula (III-A) are subsequently modified
because the modified groups would not survive formation of the
lactone itself. Through one step or multi-step art-recognized
functional group transformation chemistries, lactone compounds
represented by Formula (III-A) can be transformed to modified
lactone compounds having unique substituted groups. Such unique
substituted groups include, but are not limited to, lengthening
groups (or L groups), groups that are not present in commercially
available starting materials and groups that don't survive lactone
formation chemistry. The transformation chemistries include, but
are not limited to, Friedel-Crafts reactions, palladium-catalyzed
cross couplings, cyanation chemistries, etherifications, C--H bond
activation chemistries, borylation chemistries, esterifications,
amidations, oxidation chemistries, and reduction chemistries. For
purposes of non-limiting illustration, the modification of lactone
compounds represented by Formula (III-A) is shown in Examples 3, 4
and 5 further herein, in which the starting lactones were converted
in-situ to modified lactones having new substituents, such as but
not limited to, 9-(2-phenylpropan-2-yl), before other reactions
were undertaken.
[0114] The acid ester represented by Formula (1) of Scheme-5 can be
prepared in accordance with art-recognized methods. With some
embodiments, the acid ester represented by Formula (1) is prepared
by a reaction between a ketone represented by Formula (4) and a
succinic acid diester represented by Formula (5), as represented by
Scheme-6 of FIG. 6.
[0115] With reference to Scheme-6 of FIG. 6, the ketone represented
by Formula (4) is reacted with a succinic acid diester represented
by Formula (5), in which each R.sub.30 is as described previously
herein (e.g., each R.sub.30 can be ethyl), in the presence of a
strong base, such as an alkali metal alkoxide, such as NaOR.sub.30
(e.g., sodium ethoxide). The reaction of Scheme-6 is conducted
under appropriate conditions, such as under reflux at a temperature
of the boiling point of the solvent, under an inert atmosphere, and
in the presence of an appropriate solvent, such as tetrahydrofuran
or toluene. Workup of the reaction represented by Scheme-6 is
conducted, with some embodiments, in accordance with art-recognized
procedures.
[0116] With further reference to Schemes-(5) and (6) of FIGS. 5 and
6, Ring-A, n, R.sup.1-R.sup.5, and Y, are each as described herein
with reference to Formulas (I-A) and (III-A).
[0117] The intermediate compounds of the present invention, such as
represented by Formula (I-A), are for preparation of a photochromic
compound, with some embodiments. In accordance with some
embodiments, the intermediate compounds of the present invention
are used to prepare photochromic fused ring indenopyran compounds,
such as represented by the following Formula (I-A-PC):
##STR00026##
With reference to Formula (I-A-PC), Ring-A, n, R.sup.1-R.sup.5,
Z.sub.1, Z.sub.2, and Z.sub.3 are each as described herein with
reference to Formula (I-A).
[0118] With further reference to Formula (I-A-PC), B and B' are
each independently selected from, hydrogen, hydrocarbyl and
substituted hydrocarbyl each optionally and independently
interrupted with at least one of --O--, --S--, --C(O)--, --C(O)O--,
--S(O)--, --SO.sub.2--, --N.dbd.N--, --N(R.sub.11')-- where
R.sub.11' is selected from hydrogen, hydrocarbyl or substituted
hydrocarbyl, --Si(OR.sub.8').sub.w(R.sub.8').sub.t--, where w and t
are each independently selected from 0 to 2, provided that the sum
of w and t is 2, and each R.sub.8' is independently selected from
hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations
of two or more thereof.
[0119] With additional reference to Formula (I-A-PC), and in
accordance with some further embodiments, B and B' are each
independently selected from, hydrogen, unsubstituted aryl,
substituted aryl, unsubstituted heteroaryl, and substituted
heteroaryl, or B and B' taken together form a ring structure
selected from unsubstituted fluoren-9-ylidene, substituted
fluoren-9-ylidene, saturated spiro-monocyclic hydrocarbon ring,
saturated spiro-bicyclic hydrocarbon ring, and spiro-tricyclic
hydrocarbon ring.
[0120] In accordance with some further embodiments, B and B' of
Formula (I-A-PC) are each independently selected from: an aryl
group that is mono-substituted with a reactive substituent or a
compatiblizing substituent; a substituted phenyl; a substituted
aryl; a substituted 9-julolindinyl; a substituted heteroaromatic
group chosen from pyridyl, furanyl, benzofuran-2-yl,
benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl,
dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl,
and fluorenyl, wherein the phenyl, aryl, 9-julolindinyl, or
heteroaromatic substituent is a reactive substituent R; an
unsubstituted, mono-, di-, or tri-substituted phenyl or aryl group;
9-julolidinyl; or an unsubstituted, mono- or di-substituted
heteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl,
benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl,
dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl,
and fluorenyl. With some further embodiments, each of the phenyl,
aryl and heteroaromatic substituents are each independently
selected from: hydroxyl, a group --C(.dbd.O)R.sub.21, wherein
R.sub.21 is --OR.sub.22, --N(R.sub.23)R.sub.24, piperidino, or
morpholino, wherein R.sub.22 is allyl, C.sub.1-C.sub.20 alkyl,
phenyl, mono(C.sub.1-C.sub.20)alkyl substituted phenyl,
mono(C.sub.1-C.sub.20)alkoxy substituted phenyl,
phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkyl
substituted phenyl(C.sub.1-C.sub.20)alkyl,
mono(C.sub.1-C.sub.20)alkoxy substituted
phenyl(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20
alkoxy(C.sub.2-C.sub.20)alkyl or C.sub.1-C.sub.20 haloalkyl,
R.sub.23 and R.sub.24 are each independently C.sub.1-C.sub.20
alkyl, C.sub.5-C.sub.10 cycloalkyl, phenyl or substituted phenyl,
the phenyl substituents being C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy, and said halo substituent is chloro or
fluoro, aryl, mono(C.sub.1-C.sub.20)alkoxyaryl,
di(C.sub.1-C.sub.20)alkoxyaryl, mono(C.sub.1-C.sub.20)alkylaryl,
di(C.sub.1-C.sub.20)alkylaryl, haloaryl, C.sub.3-C.sub.10
cycloalkylaryl, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10
cycloalkyloxy, C.sub.3-C.sub.10
cycloalkyloxy(C.sub.1-C.sub.20)alkyl, C.sub.3-C.sub.10
cycloalkyloxy(C.sub.1-C.sub.20)alkoxy, aryl(C.sub.1-C.sub.20)alkyl,
aryl(C.sub.1-C.sub.20)alkoxy, aryloxy,
aryloxy(C.sub.1-C.sub.20)alkyl, aryloxy(C.sub.1-C.sub.20)alkoxy,
mono- or di(C.sub.1-C.sub.20)alkylaryl(C.sub.1-C.sub.20)alkyl,
mono- or di-(C.sub.1-C.sub.20)alkoxyaryl(C.sub.1-C.sub.20)alkyl,
mono- or di-(C.sub.1-C.sub.20)alkylaryl(C.sub.1-C.sub.20)alkoxy,
mono- or di-(C.sub.1-C.sub.20)alkoxyaryl(C.sub.1-C.sub.20)alkoxy,
amino, mono- or di-(C.sub.1-C.sub.20)alkylamino, diarylamino,
piperazino, N--(C.sub.1-C.sub.20)alkylpiperazino, N-arylpiperazino,
aziridino, indolino, piperidino, morpholino, thiomorpholino,
tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl,
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 haloalkyl,
C.sub.1-C.sub.20 alkoxy,
mono(C.sub.1-C.sub.20)alkoxy(C.sub.1-C.sub.20)alkyl, acryloxy,
methacryloxy, or halogen.
[0121] With some further embodiments, B and B' of Formula (I-A-PC)
are each independently selected from an unsubstituted or
mono-substituted group chosen from pyrazolyl, imidazolyl,
pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl,
phenoxazinyl, phenazinyl, and acridinyl, in which each of the
substituents being C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy,
phenyl, or halogen.
[0122] With some additional embodiments, B and B' of Formula
(I-A-PC) are each independently selected from a group represented
by one of the following Formulas (XIVA) or (XIVB):
##STR00027##
Independently for Formulas (XIVA) and (XIVB), K is --CH.sub.2-- or
--O--, and M is --O-- or substituted nitrogen, provided that when M
is substituted nitrogen, K is --CH.sub.2--, the substituted
nitrogen substituents being hydrogen, C.sub.1-C.sub.20 alkyl, or
C.sub.1-C.sub.20 acyl, each R.sub.25 being independently chosen for
each occurrence from C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20
alkoxy, hydroxy, and halogen, R.sub.26 and R.sub.27 each being
independently hydrogen or C.sub.1-C.sub.20 alkyl, and u is an
integer ranging from 0 to 2.
[0123] With some additional embodiments, B and B' of Formula
(I-A-PC) are each independently selected from a group represented
by the following Formula (XV):
##STR00028##
With reference to Formula (XV), R.sub.28 is hydrogen or
C.sub.1-C.sub.20 alkyl, and R.sub.29 is an unsubstituted, mono-, or
di-substituted group chosen from naphthyl, phenyl, furanyl, and
thienyl, wherein the substituents are C.sub.1-C.sub.20 alkyl,
C.sub.1-C.sub.20 alkoxy, or halogen.
[0124] In accordance with some alternative embodiments, B and B' of
Formula (I-A-PC) taken together form one of a fluoren-9-ylidene,
mono-, or di-substituted fluoren-9-ylidene, each of said
fluoren-9-ylidene substituents being independently chosen from
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, and halogen.
[0125] In accordance with some additional embodiments, B and B' of
Formula (I-A-PC) are each independently selected from phenyl, and
phenyl substituted with at least one of fluoro, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkoxy, morpholino, piperidino, and
pyrrolidino.
[0126] With some embodiments, the photochromic fused ring
indenopyran compound represented by Formula (I-A-PC) is prepared by
reacting the intermediate compound represented by Formula (I-A)
with a propargyl alcohol represented by the following Formula
(XI):
##STR00029##
With reference to Formula (XI), B and B' are as described herein
with reference to Formula (I-A-PC).
[0127] With some embodiments, the photochromic fused ring
indenopyran compound, such as represented by Formula (I-A-PC), is
formed by reacting or coupling the propargyl alcohol represented by
Formula XI and the intermediated compound represented by Formula
(I-A), in the presence of a catalytic amount of a protonic acid,
such as dodecyl benzene sulfonic acid (DBSA) or para-toluene
sulfonic acid (pTSA), in a suitable solvent, such as a haloalkyl
(e.g., trichloromethane), under an inert atmosphere (e.g., a
nitrogen sweep), and at a temperature range of from 0.degree. C. to
the boiling point of the solvent, such as from 0.degree. C. to
55.degree. C., or from 10.degree. C. to 45.degree. C., or from
20.degree. C. to 25.degree. C.
[0128] In accordance with some embodiments, the fused ring indeno
compounds prepared by the methods of the present invention and
certain intermediate compounds are used to prepare photochromic
fused ring indeno-naphtho-pyran compounds, such as represented by
the following Formula (I-B-PC):
##STR00030##
With reference to Formula (I-B-PC), n, R.sup.1-R.sup.5,
Z.sub.1-Z.sub.3, B and B' are each as described herein with
reference to Formulas (I-A) and (I-A-PC). With further reference to
Formula (I-B-PC), the ring that includes Z.sub.1-Z.sub.3 is bonded
to both ring positions as depicted in Formula (I-B-PC).
[0129] With some embodiments, the photochromic fused ring
indenopyran compound represented by Formula (I-B-PC) is prepared by
reacting the intermediate compound represented by Formula (I-B)
with the propargyl alcohol represented by Formula (XI).
[0130] The photochromic compounds, with some embodiments, are used
to prepare photochromic articles that include one or more such
photochromic compounds. The photochromic articles are, with some
embodiments, prepared by art-recognized methods, such as by
imbibition methods, cast-in-place methods, coating methods, in-mold
coating methods, over-mold methods, and lamination methods.
[0131] With some embodiments the photochromic articles are selected
from ophthalmic articles, display articles, windows, mirrors, and
active liquid crystal cell articles, and passive liquid crystal
cell articles. With some further embodiments, the photochromic
article is selected from ophthalmic articles, and the ophthalmic
articles are selected from corrective lenses, non-corrective
lenses, contact lenses, intra-ocular lenses, magnifying lenses,
protective lenses, and visors. With some further embodiments, the
photochromic article is selected from display articles, and the
display articles are selected from screens, monitors, and security
elements.
[0132] The present invention is more particularly described in the
following examples, which are intended as illustrative only, since
numerous modifications and variations therein will be apparent to
those skilled in the art.
EXAMPLES
Example 1
Step 1
[0133] Into a flask containing benzoyl chloride (206 g) and
dichloromethane (2 L) was added aluminum chloride (200 g) while
stirring. After 30 minutes at ambient temperature the flask was
placed in a water bath and a condenser was connected through which
2-methylfuran (210 mL) was added dropwise over 30 minutes. The
resulting mixture was stirred for 7 hours then carefully poured
into cold water (3 L). The organic layer was collected, washed with
water and concentrated to afford
(5-methylfuran-2-yl)(phenyl)methanone as an oily product (220
g).
Step 2
[0134] The product of Step 1 (220 g), dimethyl succinate (242 mL)
and toluene (2.5 L) were added to a reaction flask equipped with a
mechanical stirrer, a solid addition funnel and a Nitrogen blanket.
Potassium t-butoxide (176 g) was added through the solid addition
funnel and the mixture was stirred at room temperature for 3 hours.
The resulting mixture was poured into water (2 L) and the aqueous
layer was collected. The toluene layer was extracted with water
(200 mL). The aqueous layers were combined and washed with toluene.
Aqueous HCl (3N) was added to the water solution to adjust the pH
to 5. The resulting solution was extracted with ethyl acetate. The
ethyl acetate layer was then washed with brine (500 mL) and
concentrated. The residue was then purified through a silica gel
plug eluting with a mixture of 1/1 toluene/ethyl acetate,
collecting the fractions containing the product. After evaporation
of the solvents, a dense oily material was obtained (203 g).
Step 3
[0135] Anhydrous lanthanum (III) chloride (91 g) was ground to very
fine powder then mixed with lithium chloride (47 g) and dry THF
(1.5 L) in a 5 L three-neck flask equipped with a mechanical
stirrer and an addition funnel. The mixture was refluxed until
completely dissolved. The product from Step 2 (54 g) was dissolved
in the mixture, then cooled to -5.degree. C. A solution of 3 M
methyl magnesium chloride in dry THF (375 mL) was placed in the
addition funnel. The first 100 mL of the Grignard was added to the
mixture slowly, observing gas bubbles and an exotherm. After
reducing the temperature back to -5.degree. C., the remainder of
the Grignard was added over 3 minutes. After stirring 30 minutes at
-5.degree. C., the ice bath was removed and the mixture was stirred
at room temperature for one hour. The reaction mixture was then
poured into a flask containing cold water (350 mL) and the pH
adjusted to 4 using 12 M HCl (25 mL). The water layer was discarded
and the organic layer was washed twice with brine and concentrated
to dry. The resulting solid was re-dissolved in toluene and
purified through a silica gel plug eluting with toluene. The clear
solution was concentrated to dryness to obtain a dark oily product
(41 g). .sup.1H NMR showed that the product had a structure
consistent with .about.1/1 mixture of E/Z isomers of
beta-((5-methylfuran-2-yl)(phenyl)methylene)-gamma,gamma-dimethyl-gamma-b-
utyrolactone.
Step 4
[0136] The product from step 3 (5 g) and N-(4-bromophenyl)maleimide
(5 g) were dissolved in acetic anhydride (50 mL) followed by
addition of bismuth triflate (0.8 g). The reaction mixture was
heated at 70.degree. C. for 3 hours. The solvent was then removed
by evaporation, and the resulting residue re-dissolved in
dichloromethane and washed with water (100 mL). The organic layer
was collected and purified through a silica gel plug eluting with a
mixture of 5/1 hexanes/ethyl acetate, collecting the fractions
containing the product. Removal of solvent yielded a solid product
(9 g). .sup.1H NMR showed that the product had a structure
consistent with
11-(4-bromophenyl)-10,12-dioxo-7,7,9-trimethyl-7,10,11,12-tetrahydropyrro-
lo[3',4':4,5]indeno[3,2-a]naphthalen-5-yl acetate.
Example 2
[0137] The procedure from Example 1 was followed except maleic
anhydride was used in place of N-(4-bromophenyl)maleimide to yield
a yellow solid. .sup.1H NMR showed that the product had a structure
consistent with
10,12-dioxo-7,7,9-trimethyl-10,12-dihydro-7H-furo[3',4':4,5]indeno[3,2-a]-
naphthalen-5-yl acetate.
Example 3
Step 1
[0138] To a stirred mixture of aluminum chloride (187 g) and
dichloromethane (1 L) at 0.degree. C., was added a mixture of
2-furoyl chloride (160 g) and dichloromethane (100 ml) dropwise at
a rate such that the temperature was maintained between 0.degree.
and 40.degree. C., approximately 30 minutes. The mixture was
stirred for an additional 30 minutes, then transferred to an
addition funnel. The solution was added dropwise to a stirred
solution of anisol (150 g) and dichloromethane (100 ml) in an ice
bath over a period of one hour, maintaining a temperature below
20.degree. C. After the addition, the mixture was stirred at
0.degree. C. for 30 minutes, warmed to ambient temperature and
stirred for one additional hour then poured onto ice (1 Kg). To the
mixture was added 3N HCl (200 ml) and the mixture stirred at room
temperature for two hours, after which the organic phase was
collected. To the collected organic solution was added 2N aqueous
NaOH (500 ml) and the mixture was stirred for two hours. The
organic layer was collected, dried over magnesium sulfate and
concentrated by evaporation to yield a clear liquid (278 g).
.sup.1H NMR showed that the product had a structure consistent with
furan-2-yl(4-methoxyphenyl)methanone.
Step 2
[0139] The product of Step 1 (80 g), dimethyl succinic ester (115
g) and toluene (800 ml) were placed in a three-neck 3 L flask
equipped with a mechanical stirrer. Potassium t-butoxide (67 g) was
added in batches over a 30 minute period. An exothermic reaction
was observed along with the formation of a large amount of
precipitate. After a one hour hold, water (800 mL) was added and
the mixture transferred to a separatory funnel. The aqueous phase
was collected and washed twice with toluene (200 mL). The pH was
adjusted to .about.2 using 3N HCl, resulting in the separation of a
large amount of oil. To the mixture was added ethyl acetate (500
mL). After stirring at ambient temperature for 10 minutes, the
organic layer was collected, washed with brine and dried over
MgSO.sub.4. After concentration, the crude product was purified
through a silica gel plug with the use of a gradient of 10/90 to
60/40 ethyl acetate/hexane as the eluent. A viscous oil (95 g) was
obtained. .sup.1H NMR showed that the obtained product (62 g) had a
structure consistent with .about.1/1 Z/E mixture of
4-(furan-2-yl)-3-(methoxycarbonyl)-4-(4-methoxyphenyl)but-3-enoic
acid.
Step 3
[0140] A stock solution was prepared by mixing anhydrous lanthanum
(III) chloride powder (147 g) and lithium chloride (76.2 g) in dry
THF (2 L) and stirring for 3 days. The product of Step 2 (50 g) was
dissolved in the stock solution (1 L) and cooled to 0.degree. C. A
solution of 2 M butyl magnesium chloride in THF (320 mL) was placed
in the addition funnel. The first 30% of the Grignard was added
slowly to the mixture, during which an exotherm was observed. Upon
restoring the temperature to 0.degree. C., the remainder of the
Grignard was added over one minute. After stirring one hour at
0.degree. C. and an additional hour at room temperature, the
mixture was poured into ice water (0.5 L), and the pH adjusted to
.about.3 using 12 N HCl (.about.70 ml). The mixture turned clear
with formation of two layers. The aqueous layer was discarded. The
organic layer was washed with brine three times then concentrated
to dryness. The crude product was purified through a silica gel
plug with the use of toluene as eluent to yield a viscous oil (32
g). .sup.1H NMR showed that the product had a structure consistent
with a mixture of .about.1/1 E/Z isomers of
beta-((4-methoxyphenyl)(furan-2-yl)methylene)-gamma,gamma-dibutyl-gamma-b-
utyrolactone.
Step 4
[0141] To a solution of maleic anhydride (0.8 g) in acetic
anhydride (5 ml) was added the product from Step 3 (0.76 g),
2-phenylpropan-2-ol (0.7 g) and bismuth triflate (0.16 g). The
mixture was stirred at room temperature for 48 hours followed by
removal of solvent. The residue was purified by column separation
using a CombiFlash.RTM. Rf from Teledyne ISCO to yield a viscous
yellow oil (0.32 g). .sup.1H NMR showed that the product had a
structure consistent with
10,12-dioxo-7,7-dibutyl-3-methoxy-9-(2-phenylpropan-2-yl)-10,12-dihydro-7-
H-furo[3',4':4,5]indeno[3,2-a]naphthalen-5-yl acetate.
Example 4
Step 1
[0142] To a stirred mixture of benzoyl chloride (120 g), furan (100
mL) and dichloromethane (1 L) at 0.degree. C. was added aluminum
chloride (130 g) over one hour. The mixture was stirred at room
temperature for two hours then poured slowly into water (1 L), then
passed through Celite to remove the resulting brown precipitate.
The organic layer was collected and concentrated. The crude product
was purified by silica gel chromatography eluting with 2/8 ethyl
acetate/hexane to yield a viscous oil (50 g). .sup.1H NMR showed
that the product had a structure consistent with
furan-2-yl(phenyl)methanone.
Step 2
[0143] The procedure from Step 2 of Example 3 was followed except
the product from Step 1 of this Example was used in place of the
product from Step 1 of Example 3.
Step 3
[0144] The procedure from Step 3 of Example 3 was followed except
methyl magnesium chloride was used in place of butyl magnesium
chloride.
Step 4
[0145] The procedure from Step 4 of Example 3 was followed except
N-(4-bromophenyl)maleimide was used in place of maleic anhydride.
.sup.1H NMR showed that the product had a structure consistent with
11-(4-bromophenyl)-10,12-dioxo-7,7-dimethyl-9-(2-phenylpropan-2-yl)-7,10,-
11,12-tetrahydropyrrolo[3',4':4,5]indeno[3,2-a]naphthalen-5-yl
acetate.
Example 5
[0146] The procedures from Example 4 were followed except maleic
anhydride was used in place of N-(4-bromophenyl)maleimide in Step
4. .sup.1H NMR showed that the product had a structure consistent
with
10,12-dioxo-7,7-dimethyl-9-(2-phenylpropan-2-yl)-10,12-dihydro-7H-furo[3'-
,4':4,5]indeno[3,2-a]naphthalen-5-yl acetate.
Example 6
[0147] The product from Example 1 (3 g) was dissolved in ethanol
(70 mL) and 12 M HCl (0.2 mL) was added. The mixture was refluxed
for 1 hour then cooled to ambient temperature. The solvent was
removed by evaporation. The residue was dissolved in
dichloromethane (100 mL), washed once with water (100 mL) and
concentrated to dryness. Solid product (2.6 g) was obtained.
.sup.1H NMR showed that the product had a structure consistent with
11-(4-bromophenyl)-10,12-dioxo-7,7,9-trimethyl-7,10,11,12-tetrahydro-
pyrrolo[3',4':4,5]indeno[3,2-a]naphthalen-5-ol.
Example 7
[0148] The procedures from Example 6 were followed except the
product from Example 4 was used in place of the product from
Example 1. .sup.1H NMR showed that the product had a structure
consistent with
11-(4-bromophenyl)-10,12-dioxo-7,7-dimethyl-9-(2-phenylpropan-2-yl)-7,10,-
11,12-tetrahydropyrrolo[3',4':4,5]indeno[3,2-a]naphthalen-5-ol.
Example 8
[0149] The procedures from Example 6 were followed except the
product from Example 5 was used in place of the product from
Example 1. .sup.1H NMR showed that the product had a structure
consistent with
10,12-dioxo-7,7-dimethyl-9-(2-phenylpropan-2-yl)-10,12-dihydro-7H-furo[3'-
,4':4,5]indeno[3,2-a]naphthalen-5-ol.
Example 9
[0150] A solution containing the product from Example 1 (1 g),
4-(trans-4-pentylcyclohexyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-
-2-yl)phenyl)benzamide (1 g) and K.sub.2CO.sub.3 (1.5 g) in
1,2-dimethoxyethane (70 mL) and water (30 mL) was stirred and
sparged with Nitrogen for 10 minutes. Then
bis(triphenylphosphine)palladium(II)dichloride (0.13 g) was added
and the reaction mixture was heated to reflux for 8 hours. Upon
cooling, the solution was extracted with ethyl acetate (100 mL).
The organic phase was collected and concentrated, and the residue
purified through a silica gel plug to yield a solid product (1.2
g). .sup.1H NMR showed that the product had a structure consistent
with
11-(4'-(4-(trans-4-pentylcyclohexyl)benzamido)-[1,1'-biphenyl])-10,12-dio-
xo-7,7,9-trimethyl-7,10,11,12-tetrahydropyrrolo[3',4':4,5]indeno[3,2-a]nap-
hthalen-5-ol.
Example 10
[0151] A mixture of the product from Example 3 (0.31 g),
4-aminophenol (0.3 g) and acetic acid (5 mL) was stirred under
reflux for two hours followed by removal of solvent. The residue
was purified by column separation using a CombiFlash Rf to yield a
yellow solid (0.23 g). .sup.1H NMR showed that the product had a
structure consistent with
11-(4-hydroxyphenyl)-10,12-dioxo-7,7-dibutyl-3-methoxy-9-(2-phenylpropan--
2-yl)-7,10,11,12-tetrahydropyrrolo[3',4':4,5]indeno[3,2-a]naphthalen-5-ol.
Example 11
[0152] The product from Example 6 (3 g) was dissolved in
dichloroethane (150 mL). To the flask was added
1-(4-butoxyphenyl)-1-phenylprop-2-yn-1-ol (2 g) and a few crystals
of p-toluenesulfonic acid. The mixture was stirred at room
temperature for three hours. The reaction mixture was washed once
with water (50 mL) and the organic residue was purified by silica
gel chromatography eluting with 4/1 hexanes/ethyl acetate. After
evaporation of the solvents, the product was further purified using
a CombiFlash Rf, yielding yellow crystals (0.9 g). .sup.1H NMR
analysis indicated that the product had a structure consistent with
10-(4-bromophenyl)-3-(4-butoxyphenyl)-12,14,14-trimethyl-9,11-dioxo-3-phe-
nyl-3,9,11,14-tetrahydropyrrolo[3',4':4,5]indeno[2',3':3,4]naphtho[1,2-b]p-
yran.
Example 12
[0153] The procedure from Example 11 was used except the product
from Example 7 was used in place of the product from Example 6 in
Step 1, and 1-(4-methoxyphenyl)-1-phenylprop-2-yn-1-ol was used in
place of 1-(4-butoxyphenyl)-1-phenylprop-2-yn-1-ol in Step 2.
.sup.1H NMR analysis showed the product had a structure consistent
with
10-(4-bromophenyl)-3-(4-methoxyphenyl)-14,14-dimethyl-9,11-dioxo-3-phenyl-
-12-(2-phenylpropan-2-yl)-3,9,11,14-tetrahydropyrrolo[3',4':4,5]indeno[2',-
3':3,4]naphtho[1,2-b]pyran.
Example 13
[0154] The procedure from Example 11 was used except that the
product from Example 8 was placed in place of the product from
Example 6 in Step 1, and 1-(4-methoxyphenyl)-1-phenylprop-2-yn-1-ol
was used in place of 1-(4-butoxyphenyl)-1-phenylprop-2-yn-1-ol in
Step 2. .sup.1H NMR analysis showed the product had a structure
consistent with
3-(4-methoxyphenyl)-14,14-dimethyl-9,11-dioxo-3-phenyl-12-(2-(2-phenylpro-
pan-2-yl))-3,9,11,14-tetrahydrofuro[3',4':4,5]indeno[2',3':3,4]naphtho[1,2-
-b]pyran.
Example 14
[0155] The procedure from Example 11 was used except that the
product from Example 9 was placed in place of the product from
Example 6 in Step 1, and 1-(4-methoxyphenyl)-1-phenylprop-2-yn-1-ol
was used in place of 1-(4-butoxyphenyl)-1-phenylprop-2-yn-1-ol in
Step 2. .sup.1H NMR analysis showed the product had a structure
consistent with
3-(4-methoxyphenyl)-14,14-dimethyl-9,11-dioxo-3-phenyl-12-(2-(2-phenylpro-
pan-2-yl))-3,9,11,14-tetrahydrofuro[3',4':4,5]indeno[2',3':3,4]naphtho[1,2-
-b]pyran.
[0156] The present invention has been described with reference to
specific details of particular embodiments thereof. It is not
intended that such details be regarded as limitations upon the
scope of the invention except insofar as to the extent that they
are included in the accompanying claims.
* * * * *