US4207253A
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Method of making copolymerizable, ultraviolet light absorber (2-cyano-3,3-diphenylacryloxy) alkylene acrylic acid esters
Assignee: ISP Investments LLC
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Filing: 1979-03-01
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Granted: 1980-06-10
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Expires: 1999-03-01
Abstract
Abstract This invention relates to a method of making in high yield light absorber compounds which are (2-cyano-3,3-diphenylacryloxy) alkylene acrylic acid esters having the formula: ##STR1## where (Ar) 1 and (Ar) 2 are aromatic carbocyclic nuclei of the benzene and naphthalene series and are independently selected from phenyl or phenyl substituted with alkyl, halo, alkoxy, carboxy, carbalkoxy, cyano, acetyl, benzoyl, phenyl, alkyl phenyl, phenoxy phenyl, alkyl substituted phenoxy, or alkoxy phenyl substituted phenyl, and naphthyl; X is alkylene, C 2 -C 17 , unsubstituted or substituted with halo, cyano, alkyl, alkoxy, alkoxyalkyl, or alkoxyalkyleneoxy, C 1 -C 6 ; and Y is copolymerizable radical selected from acryloyl, alkylacryloyl, acryloxyalkyl, acryloxyhydroxyalkyl and alkylacryloxyhydroxyalkyl, C 3 -C 12 . The method comprises: (a) acylating a hydroxyalkylene cyanoacetate with an acylating agent to form an acylated intermediate whose hydroxy radical is protected by an acyl group which is convertible to hydroxy by hydrolysis, (b) condensing the acyl intermediate with a benzophenone, (c) hydrolyzing the condensed compound to form the corresponding condensed hydroxy compound; and, (d) esterifying the hydroxy compound with an acryloyl halide or an acrylic acid to provide the desired product.
Inventors
- 👤 Donald H. Lorenz
- 👤 Bruce A. Gruber
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 00:22
CPC Classifications
C; C07; C07C; C07C255/00; C08; C08F; C08F20/00; C08F20/02; C08F20/10; C08F20/34; C08F20/36
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
239 words
A method of making copolymerizable ultraviolet light absorber (2-cyano-3,3-diphenylacryloxy) alkylene acrylic acid esters in high yield having the formula: ##STR12## where (Ar) 1 and (Ar) 2 are aromatic carbocyclic nuclei of the benzene and naphthalene series and are independently selected from phenyl or phenyl substituted with alkyl, halo, alkoxy, carboxy, carbalkoxy, cyano, acetyl, benzoyl, phenyl, alkyl phenyl, phenoxy phenyl, alkyl substituted phenoxy, or alkoxy phenyl substituted phenyl, and naphthyl; X is alkylene, C 2 -C 17 , unsubstituted or substituted with halo, cyano, alkyl, alkoxy, alkoxyalkyl, or alkoxyalkyleneoxy, C 1 -C 6 ; and, Y is copolymerizable radical selected from acryloyl, alkylacryoyl, acryloxyalkyl, acryloxyhydroxyalkyl and alkylacryloxyhydroxyalkyl, C 3 -C 12 , which comprises the steps of: (a) acylating a hydroxyalkylene cyanoacetate having the formula: ##STR13## where X is as defined above, with an acetyl acylating agent capable of reacting with the hydroxy group to form an acetyl acylated intermediate which is convertible to hydroxy by hydrolysis, (b) condensing the acetyl acylated intermediate with a benzophenone having the formula: ##STR14## where (Ar) 1 and (Ar) 2 are as defined above, to form a condensed intermediate which is ##STR15## (c) hydrolyzing the condensed intermediate to form the corresponding condensed hydroxy compound which is ##STR16## and; (d) esterifying the condensed hydroxy compound with an acryloyl halide or acrylic acid having the formula: YZ where Y is as defined above and Z is a halide or hydroxyl group, to form said desired compounds.
Claim 2
Independent Claim
239 words
A method of making copolymerizable ultraviolet light absorber (2-cyano-3,3-diphenylacryloxy) alkylene acrylic acid esters in high yield having the formula: ##STR12## where (Ar) 1 and (Ar) 2 are aromatic carbocyclic nuclei of the benzene and naphthalene series and are independently selected from phenyl or phenyl substituted with alkyl, halo, alkoxy, carboxy, carbalkoxy, cyano, acetyl, benzoyl, phenyl, alkyl phenyl, phenoxy phenyl, alkyl substituted phenoxy, or alkoxy phenyl substituted phenyl, and naphthyl; X is alkylene, C 2 -C 17 , unsubstituted or substituted with halo, cyano, alkyl, alkoxy, alkoxyalkyl, or alkoxyalkyleneoxy, C 1 -C 6 ; and, Y is copolymerizable radical selected from acryloyl, alkylacryoyl, acryloxyalkyl, acryloxyhydroxyalkyl and alkylacryloxyhydroxyalkyl, C 3 -C 12 , which comprises the steps of: (a) acylating a hydroxyalkylene cyanoacetate having the formula: ##STR13## where X is as defined above, with an acetyl acylating agent capable of reacting with the hydroxy group to form an acetyl acylated intermediate which is convertible to hydroxy by hydrolysis, (b) condensing the acetyl acylated intermediate with a benzophenone having the formula: ##STR14## where (Ar) 1 and (Ar) 2 are as defined above, to form a condensed intermediate which is ##STR15## (c) hydrolyzing the condensed intermediate to form the corresponding condensed hydroxy compound which is ##STR16## and; (d) esterifying the condensed hydroxy compound with an acryloyl halide or acrylic acid having the formula: YZ where Y is as defined above and Z is a halide or hydroxyl group, to form said desired compounds.
Claim 3
Dependent Claim
16 words
A method according to claim 1 in which both (Ar) 1 and (Ar) 2 are phenyl.
Claim 4
Dependent Claim
16 words
A method according to claim 1 in which X is alkylene, C 2 -C 6 .
Claim 5
Dependent Claim
15 words
A method according to claim 1 in which Y is acryloyl, methacryloyl, 3-acryloxy-2-hydroxypropyl or 3-methacryloxy-2-hydroxypropyl.
Claim 6
Dependent Claim
31 words
A method according to claim 1 in which both (Ar) 1 and (Ar) 2 are phenyl, X is alkylene, C 2 -C 6 and Y is acryloyl, methacryloyl, 3-acryoxy-2-hydroxypropyl or 3-methacryloxy-2-hydroxypropyl.
Claim 7
Dependent Claim
21 words
A method according to claim 1 in which in step (c) the hydrolysis is carried out under acid conditions in alcohol.
Claim 8
Dependent Claim
16 words
A method according to claim 1 in which in step (d), YZ is an acryloyl halide.
Claim 9
Dependent Claim
16 words
A method according to claim 1 in which in step (d), YZ is an acrylic acid.
Claim 10
Dependent Claim
29 words
A method according to claim 1 in which in step (d) an excess of the acryloyl halide or acrylic acid over a 1:1 molar ratio of reactants is used.
Claim 11
Dependent Claim
29 words
A method according to claim 1 in which step (d) is carried out with an acryloyl chloride or acryloyl bromide in a solvent in the presence of a base.
Claim 12
Dependent Claim
54 words
A method according to claim 1 in which step (d) is carried out with an acrylic acid in an inert solvent which forms an azeotrope with the water by-product of the reaction which can be removed by distillation, and in the presence of a polymerization inhibitor to prevent polymerization of the acrylic acid reactant.
Claim 13
Independent Claim
181 words
A method of making intermediates in the manufacture of copolymerizable ultraviolet light absorber (2-cyano-3,3-diphenylacryloxy) alkylene acrylic acid esters, said intermediates having the formula: ##STR17## where (Ar) 1 and (Ar) 2 are aromatic carbocyclic nuclei of the benzene and naphthalene series and are independently selected from phenyl or phenyl substituted with alkyl, halo, alkoxy, carboxy, carbalkoxy, cyano, acetyl, benzoyl, phenyl, alkyl phenyl, phenoxy phenyl, alkyl substituted phenoxy, or alkoxy phenyl substituted phenyl, and naphthyl; and X is alkylene, C 2 -C 17 , unsubstituted or substituted with halo, cyano, alkyl, alkoxy, alkoxyalkyl, or alkoxyalkyleneoxy, C 1 -C 6 ; which comprises the steps of: (a) acetylating a hydroxyalkylene cyanoacetate having the formula: ##STR18## where X is as defined above, with an acetylating agent capable of reacting with the hydroxy group to form an acetyl compound which is convertible to hydroxy by hydrolysis, (b) condensing the acetyl compound with a benzophenone having the formula: ##STR19## where (Ar) 1 and (Ar) 2 are as defined above, to form a condensed compound which is ##STR20## (c) hydrolyzing the condensed compound to form the desired intermediate.
Claim 14
Independent Claim
181 words
A method of making intermediates in the manufacture of copolymerizable ultraviolet light absorber (2-cyano-3,3-diphenylacryloxy) alkylene acrylic acid esters, said intermediates having the formula: ##STR17## where (Ar) 1 and (Ar) 2 are aromatic carbocyclic nuclei of the benzene and naphthalene series and are independently selected from phenyl or phenyl substituted with alkyl, halo, alkoxy, carboxy, carbalkoxy, cyano, acetyl, benzoyl, phenyl, alkyl phenyl, phenoxy phenyl, alkyl substituted phenoxy, or alkoxy phenyl substituted phenyl, and naphthyl; and X is alkylene, C 2 -C 17 , unsubstituted or substituted with halo, cyano, alkyl, alkoxy, alkoxyalkyl, or alkoxyalkyleneoxy, C 1 -C 6 ; which comprises the steps of: (a) acetylating a hydroxyalkylene cyanoacetate having the formula: ##STR18## where X is as defined above, with an acetylating agent capable of reacting with the hydroxy group to form an acetyl compound which is convertible to hydroxy by hydrolysis, (b) condensing the acetyl compound with a benzophenone having the formula: ##STR19## where (Ar) 1 and (Ar) 2 are as defined above, to form a condensed compound which is ##STR20## (c) hydrolyzing the condensed compound to form the desired intermediate.
References Cited (Backward Citations)
US3644466A
Cited
US3993684A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-06-10 | 1983-12-10 | 1984-06-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-06-10 | 1987-12-10 | 1988-06-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-06-10 | 1991-12-10 | 1992-06-10 | $7700.00 | Window Closed / Lapsed |