Method of preparing fused ring indeno compounds

Patent metadata

Field	Value
Publication number	US-9630902-B2
Application number	US-201514936715-A
Country	US
Kind code	B2
Filing date	Nov 10, 2015
Priority date	Nov 20, 2013
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

The present invention relates to methods of preparing fused ring indeno compounds that involves reacting together a dienophile and a lactone compound, in the presence of a catalyst, and a carboxylic acid anhydride. With some embodiments, the fused ring indeno compound is represented by the following Formula (I-A), the dienophile is represented by the following Formula (II-A), and the lactone compound is represented by the following Formula (III-A):

First claim

What is claimed is:

1. A method of forming a fused ring indeno compound, which is an intermediate for preparation of a photochromic compound, wherein said fused ring indeno compound is represented by Formula (I-E),

wherein,
Ring-A is selected from aryl and fused ring aryl,
n is selected from 1 to 8,
R 1 for each n is 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 2 —, —N═N—, —N(R 11 ′)— where R 11 ′ is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl, —Si(OR 8 ′) w (R 8 ′) 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 8 ′ is independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more thereof; halogen; cyano; —O—R 10 ′, or —S—R 10 ′, or —C(O)—R 10 ′ or —C(O)—OR 10 ′, wherein each R 10 ′ is independently selected from hydrogen, hydrocarbyl or substituted hydrocarbyl; perhalohydrocarbyl; and —C(O)—N(R 11 ′)(R 12 ′) or —N(R 11 ′)R 12 ′, wherein R 11 ′ and R 12 ′ are each independently selected from hydrogen, hydrocarbyl or substituted hydrocarbyl, or R 11 ′ and R 12 ′ together form a ring structure optionally including at least one heteroatom,
R 4 and R 5 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, halogen, —C(O)—N(R 14 )(R 15 ), —N(R 14 )(R 15 ), —SR 16 , and —OR 16 , where R 14 and R 15 are each independently selected from hydrogen, hydrocarbyl, and substituted hydrocarbyl, or R 14 and R 15 together form a ring, and each R 16 is independently selected from hydrocarbyl and substituted hydrocarbyl,
R 6 and R 7 are each independently selected from hydrogen, hydrocarbyl, and substituted hydrocarbyl, each optionally and independently interrupted with —O—, —S—, —N(R 11 ′)—, where R 11 ′ is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl, and
R 9 is selected from —C(O)—R 19 and —S(O)(O)R 19 , wherein R 19 is selected from hydrocarbyl, and halohydrocarbyl,

said method comprising,
(a) in a first step, reacting together maleic anhydride and a lactone compound represented by Formula (III-A), in the presence of a catalyst, and a solvent, said solvent being substantially free of reaction with water, thereby forming an acid intermediate represented by Formula (VIII-A),

wherein for said lactone compound represented by Formula (III-A) and for said acid intermediate represented by Formula (VIII-A), Ring-A, n, R 1 , R 4 , R 5 , R 6 , and R 7 are each as described with regard to said fused ring indeno compound represented by Formula (I-E), and Y of Formula (III-A) is selected from O, S, and N(R 18 ), where R 18 is selected from hydrogen, hydrocarbyl, and substituted hydrocarbyl, and
(b) in a second step, converting said acid intermediate represented by Formula (VIII-A) to said fused ring indeno compound represented by Formula (I-E) in the presence of a material selected from carboxylic acid halide, carboxylic acid anhydride, sulfonyl halide, sulfonyl anhydride, and combinations thereof.

2. The method of claim 1 wherein,
in said first step,
said catalyst is selected from at least one Lewis acid represented by Formula (V) and Formula (VI),
M y+ ( − O—SO 2 —R 20 ) y   (V)

and
M y+ (X − ) y   (VI)

 wherein independently for each of Formula (V) and Formula (VI), M represents a metal, y is the valence of the metal, R 20 for each y is independently selected from hydrocarbyl and halohydrocarbyl, and X for each y is independently selected from halogen; and
said solvent is selected from aromatic hydrocarbon solvents, haloalkyl solvents, perhaloalkyl solvents, cyano alkyl solvents, and nitro alkyl solvents.

3. The method of claim 2 wherein,
in said first step,
the metal M of Formula (V) and Formula (VI) is independently selected from Bi, B, Al, Hf, Sc, Cu, Yb, Ti, Sn, Fe, Zn, Ag, Y, In, Nb and Mg, R 20 is selected from C 1 -C 10 linear or branched alkyl, and C 1 -C 10 linear or branched perfluoroalkyl, and X is selected from I, F, Cl, and Br; and
said solvent is selected from benzene, xylene, toluene, methylene chloride, chloroform, 2-dichloroethane, acetonitrile, nitromethane and combinations of two or more thereof.

4. The method of claim 1 wherein said first step is conducted in the presence of an acid selected from alkyl sulfonic acid, aryl sulfonic acid, and combinations thereof.

5. The method of claim 4 wherein said acid is selected from p-toluene sulfonic acid, dodecylbenzenesulfonic acid, and combinations thereof.

6. The method of claim 1 further comprising, after said second step,
in a third step, hydrolyzing said intermediate represented by Formula (VIII-A) in the presence of a protonic acid or a base, thereby forming an indeno compound represented by Formula (I-F),

wherein R 12 is hydrogen.

7. The method of claim 6 wherein said protonic acid is selected from carboxylic acids, sulfonic acids, phosphoric acids, hydrogen halides, and combinations thereof.

8. The method of claim 1 wherein,
Ring-A, for Formula (I-E), Formula (III-A), and Formula (VIII-A) is selected from aryl;
R 1 , for Formula (I-E), Formula (III-A), and Formula (VIII-A), for each n is independently selected from,
hydrogen,
halogen selected from bromo, iodo, fluoro and chloro;
C 1 -C 20 linear or branched alkyl;
C 3 -C 10 cycloalkyl;
substituted or unsubstituted phenyl, the phenyl substituents being selected from halogen, halo(C 1 -C 20 )alkyl, C 1 -C 20 alkyl or C 1 -C 20 alkoxy;
—O—R 10 ′, or —S—R 10 ′ or —C(O)—R 10 ′ or —C(O)—OR 10 ′, wherein each R 10 ′ is independently selected from hydrogen, C 1 -C 20 alkyl, phenyl(C 1 -C 20 )alkyl, mono(C 1 -C 20 )alkyl substituted phenyl(C 1 -C 20 )alkyl, mono(C 1 -C 20 )alkoxy substituted phenyl(C 1 -C 20 )alkyl, (C 1 -C 20 )alkoxy(C 2 -C 20 )alkyl, C 3 -C 10 cycloalkyl, or mono(C 1 -C 20 )alkyl substituted C 3 -C 10 cycloalkyl;
—N(R 11 ′)R 12 ′, or —C(O)—N(R 11 ′)(R 12 ′), wherein R 11 ′ and R 12 ′ are each independently hydrogen, C 1 -C 20 alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, C 1 -C 20 alkylaryl, C 3 -C 10 cycloalkyl, C 4 -C 20 bicycloalkyl, C 5 -C 20 tricycloalkyl or C 1 -C 20 alkoxyalkyl, wherein said aryl group is phenyl or naphthyl, or R 11 ′ and R 12 ′ come together with the nitrogen atom to form a C 3 -C 20 hetero-bicycloalkyl ring or a C 4 -C 20 hetero-tricycloalkyl ring;
a nitrogen containing ring represented by graphic formula XIIA,

 wherein each —Y— is independently chosen for each occurrence from —CH 2 —, —CH(R 13 ′)—, —C(R 13 ′) 2 —, —CH(aryl)-, —C(aryl) 2 -, and —C(R 13 ′)(aryl)-, and Z is —Y—, —O—, —S—, —NH—, —N(R 13 ′)—, or —N(aryl)-, wherein each R 13 ′ is independently C 1 -C 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,

Assignees

• Transitions Optical Inc

Inventors

• He Meng
• Tomasulo Massimiliano
• Greene Allison
• Kumar Anil

Classifications

• C07C67/00

  Preparation of carboxylic acid esters · CPC title

• C07D209/70

  containing carbocyclic rings other than six-membered · CPC title

• C07C69/017

  Esters of hydroxy compounds having the esterified hydroxy group bound to a carbon atom of a six-membered aromatic ring · CPC title

• C07D307/77

  ortho- or peri-condensed with carbocyclic rings or ring systems · CPC title

• C07C65/17

  containing rings other than six-membered aromatic rings · CPC title