US4356325A
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Process for preparation of acetylene terminated sulfones, oligomers and precursors therefor
Assignee: Chevron USA Inc
•
Filing: 1980-11-28
•
Granted: 1982-10-26
•
Expires: 2000-11-28
Abstract
Abstract Acetylene terminated sulfones and oligomers thereof are prepared by reacting a sulfonyldiphenol with a material selected from the group consisting of a meta-dibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a potassium base to form a bis-bromophenoxydiphenyl sulfone, which is reacted with a substituted terminal acetylene compound containing at least three carbon atoms and an hydroxy group on the carbon atom adjacent to the acetylene group to form an hydroxy-acetylene terminated phenoxydiphenyl sulfone, which is then subjected to base catalyzed cleavage to form the desired acetylene terminated sulfones and oligomers. An hydroxy-arylacetylene terminated sulfone is prepared by reacting a sulfonyldiphenyl with a material selected from the group consisting of meta-dibromobenzene para-dibromobenzene and mixtures thereof in the presence of a sodium base. The resulting hydroxyphenylbromophenoxyphenyl sulfone can be: (1) reacted with a substituted terminal acetylene compound to form an hydroxy-arylacetylene terminated sulfone which in turn can be reacted with a dinitrofluorobenzene to form a dinitro-acetylene terminated sulfone which in turn can be reacted with sodium dithionite and sodium hydroxide to form a diaminoacetylene terminated sulfone; (2) reacted with a dibromobenzene to form a bis-bromophenoxydiphenyl sulfone; or (3) reacted with a bis-bromophenoxydiphenyl sulfone to form an oligomeric bromophenoxydiphenyl sulfone, which can be used to form an oligomeric actylene terminated sulfone. Metal contaminants, such as palladium and copper, used in the preparation of the acetylene terminated sulfones are removed by admixing the metal contaminated sulfone with a hydrogen halide and then contacting the admixture with an amino compound to complex the metal contaminant.
Inventors
- 👤 James J. Harrison
- 👤 Edward T. Sabourin
- 👤 Charles M. Selwitz
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-10 01:32
CPC Classifications
C; C07; C07C; C07C315/00
Claims Analysis
Total Claims: 156
Claim 1
Independent Claim
101 words
A process for the production of an acetylene terminated sulfone which comprises: (a) reacting a sulfonyldiphenol with a material selected from the group consisting of a meta-dibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a potassium base to form a bis-bromophenoxydiphenyl sulfone; (b) reacting said bis-bromophenoxydiphenyl sulfone with a substituted terminal acetylene compound containing at least three carbon atoms and an hydroxy group on the carbon atom adjacent to the acetylene group to form the corresponding hydroxy-acetylene terminated phenoxydiphenyl sulfone; and (c) subjecting said hydroxy-acetylene terminated phenoxydiphenyl sulfone to base catalyzed cleavage to form the corresponding acetylene terminated sulfone.
Claim 2
Dependent Claim
101 words
A process for the production of an acetylene terminated sulfone which comprises: (a) reacting a sulfonyldiphenol with a material selected from the group consisting of a meta-dibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a potassium base to form a bis-bromophenoxydiphenyl sulfone; (b) reacting said bis-bromophenoxydiphenyl sulfone with a substituted terminal acetylene compound containing at least three carbon atoms and an hydroxy group on the carbon atom adjacent to the acetylene group to form the corresponding hydroxy-acetylene terminated phenoxydiphenyl sulfone; and (c) subjecting said hydroxy-acetylene terminated phenoxydiphenyl sulfone to base catalyzed cleavage to form the corresponding acetylene terminated sulfone.
Claim 3
Dependent Claim
10 words
The process of claim 1, wherein said sulfonyldiphenol is 4,4'-sulfonyldiphenol.
Claim 4
Dependent Claim
15 words
The process of claim 1, wherein the dibromobenzene is a mixture of meta- and para-dibromobenzene.
Claim 5
Dependent Claim
12 words
The process of claim 1, wherein said potassium base is potassium hydroxide.
Claim 6
Dependent Claim
24 words
The process of claim 1, wherein said sulfonyldiphenol and said dibromobenzene are reacted in the presence of a catalytic amount of a copper salt.
Claim 7
Dependent Claim
20 words
The process of claim 5, wherein said copper salt is cuprous chloride, cuprous iodide, copper stearate, copper or cuprous bromide.
Claim 8
Dependent Claim
12 words
The process of claim 6, wherein said copper salt is cuprous chloride.
Claim 9
Dependent Claim
83 words
The process of claim 1, wherein said substituted terminal acetylene compound has the formula: H--C.tbd.C--Z wherein Z represents the moiety: ##STR38## wherein R 2 and R 3 can be the same or different and are selected from the group consisting of hydrogen and lower alkyl groups having from one to 4 carbon atoms, phenyl and substituted phenyl, and wherein R 2 and R 3 when taken together with the carbon atom to which they are attached form a saturated 5- or 6-membered ring.
Claim 10
Dependent Claim
14 words
The process of claim 8, wherein said terminal acetylene compound is 3-methylbutyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol.
Claim 11
Dependent Claim
12 words
The process of claim 9, wherein said terminal acetylene compound is 3-methyl-butyn-3-ol.
Claim 12
Dependent Claim
26 words
The process of claim 1, wherein said sulfonyldiphenol and said dibromobenzene are reacted at a temperature in the range of between 100° to about 250° C.
Claim 13
Dependent Claim
20 words
The process of claim 11, wherein said temperature is in the range of between about 140° and about 200° C.
Claim 14
Dependent Claim
18 words
The process of claim 1, wherein said sulfonyldiphenol and dibromobenzene are reacted in the presence of a solvent.
Claim 15
Dependent Claim
18 words
The process of claim 13, wherein said solvent is tetrahydrothiophene 1,1-dioxide, dimethylsulfoxide, N-methylpyrolidone or bis-methoxy ethoxy diethyl ether.
Claim 16
Dependent Claim
11 words
The process of claim 14, wherein said solvent is tetrahydrothiophene 1,1-dioxide.
Claim 17
Dependent Claim
42 words
A process for the production of a bis-bromophenoxydiphenyl sulfone which comprises reacting a sulfonyldiphenol with a material selected from the group consisting of a meta-dibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a potassium base to form said bis-bromophenoxydiphenyl sulfone.
Claim 18
Dependent Claim
42 words
A process for the production of a bis-bromophenoxydiphenyl sulfone which comprises reacting a sulfonyldiphenol with a material selected from the group consisting of a meta-dibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a potassium base to form said bis-bromophenoxydiphenyl sulfone.
Claim 19
Dependent Claim
18 words
The process of claim 16, wherein said sulfonyldiphenol and dibromobenzene are reacted in the presence of a solvent.
Claim 20
Dependent Claim
10 words
The process of claim 16, wherein said sulfonyldiphenol is 4,4'-sulfonyldiphenol.
Claim 21
Dependent Claim
15 words
The process of claim 16, wherein the dibromobenzene is a mixture of meta- and para-dibromobenzene.
Claim 22
Dependent Claim
12 words
The process of claim 16, wherein said potassium base is potassium hydroxide.
Claim 23
Dependent Claim
24 words
The process of claim 16, wherein said sulfonyldiphenol and said dibromobenzene are reacted in the presence of a catalytic amount of a copper salt.
Claim 24
Dependent Claim
23 words
The process of claim 21, wherein said copper salt is cuprous chloride, cuprous iodide, copper stearate, copper acetate, copper acetonylacetonate or cuprous bromide.
Claim 25
Dependent Claim
12 words
The process of claim 22, wherein said copper salt is cuprous chloride.
Claim 26
Dependent Claim
22 words
The process of claim 22, wherein the amount of said copper salt employed is from about 0.1 to about 10 mole percent.
Claim 27
Dependent Claim
22 words
The process of claim 24, wherein the amount of said copper salt employed is from about 1.0 to about 5.0 mole percent.
Claim 28
Dependent Claim
27 words
The process of claim 16, wherein said sulfonyldiphenol and said dibromobenzene are reacted at a temperature in the range of between about 100° and about 250° C.
Claim 29
Dependent Claim
20 words
The process of claim 26, wherein said temperature is in the range of between about 140° and about 200° C.
Claim 30
Dependent Claim
18 words
The process of claim 17, wherein said solvent is tetrahydrothiophene 1,1-dioxide, dimethylsulfoxide, N-methylprolidone or bis-methoxy ethoxy diethyl ether.
Claim 31
Dependent Claim
11 words
The process of claim 28, wherein said solvent is tetrahydrothiophene 1,1-dioxide.
Claim 32
Dependent Claim
17 words
The process of claim 16, wherein the reaction time is from about 1 to about 150 hours.
Claim 33
Dependent Claim
17 words
The process of claim 30, wherein the reaction time is from about 3 to about 24 hours.
Claim 34
Dependent Claim
123 words
A process for the production of an hydroxy-acetylene terminated phenoxydiphenyl sulfone which comprises reacting a bis-bromophenoxydiphenyl sulfone, wherein the bromine and oxygen moieties attached directly to the same phenyl nucleus are either meta or para, with a substituted terminal acetylene compound containing at least three carbon atoms and an hydroxy group on the carbon atom adjacent to the acetylene group having the formula: H--C.tbd.C--Z wherein Z represents the moiety: ##STR39## wherein R 2 and R 3 can be the same or different and are alkyl groups having from one to 4 carbon atoms, phenyl and substituted phenyl, and wherein R 2 and R 3 when taken together with the carbon atom to which they are attached form a saturated 5- or 6-membered ring.
Claim 35
Dependent Claim
123 words
A process for the production of an hydroxy-acetylene terminated phenoxydiphenyl sulfone which comprises reacting a bis-bromophenoxydiphenyl sulfone, wherein the bromine and oxygen moieties attached directly to the same phenyl nucleus are either meta or para, with a substituted terminal acetylene compound containing at least three carbon atoms and an hydroxy group on the carbon atom adjacent to the acetylene group having the formula: H--C.tbd.C--Z wherein Z represents the moiety: ##STR39## wherein R 2 and R 3 can be the same or different and are alkyl groups having from one to 4 carbon atoms, phenyl and substituted phenyl, and wherein R 2 and R 3 when taken together with the carbon atom to which they are attached form a saturated 5- or 6-membered ring.
Claim 36
Dependent Claim
71 words
The process of claim 32, wherein a solvent is employed wherein said solvent is an amine solvent having the formula: ##STR40## wherein R 4 , R 5 and R 6 can be the same or different and are selected from the group consisting of hydrogen and lower alkyl groups having from one to 4 carbon atoms, with the proviso that no more than one of said R groups can be hydrogen.
Claim 37
Dependent Claim
20 words
The process of claim 32, wherein said substituted terminal acetylene compound is 3-methylbutyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, 3-ethyl-1-pentyn-3-ol, 2-phenyl-3-butyn-2-ol, 1-ethynylcyclohexanol or 1-ethynylcyclopentanol.
Claim 38
Dependent Claim
13 words
The process of claim 34, wherein said substituted terminal acetylene compound is 3-methylbutyn-3-ol.
Claim 39
Dependent Claim
18 words
The process of claim 33, wherein said amine solvent is dimethylamine, trimethylamine, diethylamine, triethylamine, ethylpropylamine, ethylbutylamine or dibutylamine.
Claim 40
Dependent Claim
11 words
The process of claim 36, wherein said amine solvent is triethylamine.
Claim 41
Dependent Claim
61 words
The process of claim 32, wherein a complex catalyst is employed wherein said catalyst is a palladium complex having the formula: ##STR41## where X is bromine, iodine or chlorine, and R, R' and R" are the same or different and are selected from the group consisting of phenyl, alkyl groups having from 1 to 4 carbon atoms and substituted phenyl groups.
Claim 42
Dependent Claim
33 words
The process of claim 38, wherein said palladium complex is bis(triphenylphosphine)palladium dichloride, bis(triphenylphosphine)palladium dibromide, bis(tri-n-butylphosphine)palladium dichloride, bis(tri-t-butyl-phosphine)palladium dichloride, bis(tri-i-butylphosphine)palladium dichloride, bis(triethylphosphine)palladium dichloride, bis(tri-propylphosphine)palladium dichloride, bis(tritolylphosphine)palladium dichloride, bis(trianisylphosphine)palladium dichloride, bis(tri(chlorophenyl)phosphine)palladium dichloride or bis(tri(bromophenyl)phosphine)palladium dichloride.
Claim 43
Dependent Claim
22 words
The process of claim 38, wherein the amount of said palladium catalyst employed is from about 0.01 to about 1.0 mole percent.
Claim 44
Dependent Claim
23 words
The process of claim 40, wherein the amount of said palladium complex catalyst employed is from about 0.02 to about 0.05 mole percent.
Claim 45
Dependent Claim
14 words
The process of claim 38, wherein a promoter comprising a copper salt is employed.
Claim 46
Dependent Claim
23 words
The process of claim 42, wherein said copper salt is cuprous chloride, cuprous iodide, copper stearate, copper acetate, copper acetonylacetonate or cuprous bromide.
Claim 47
Dependent Claim
12 words
The process of claim 43, wherein said copper salt is cuprous chloride.
Claim 48
Dependent Claim
21 words
The process of claim 42, wherein the molar ratio of promoter to palladium complex is from about 0.5:1 to about 20:1.
Claim 49
Dependent Claim
21 words
The process of claim 45, wherein the molar ratio of promoter to palladium complex is from about 1:1 to about 5:1.
Claim 50
Dependent Claim
25 words
The process of claim 32, wherein the molar ratio of said bis-bromophenoxydiphenyl sulfone to said terminal acetylene compound is from about 1:0.5 to about 1:100.
Claim 51
Dependent Claim
25 words
The process of claim 47, wherein the molar ratio of said bis-bromophenoxydiphenyl sulfone to said terminal acetylene compound is from about 1:2 to about 1:5.
Claim 52
Dependent Claim
17 words
The process of claim 32, wherein the reaction temperature is from about 20° to about 200° C.
Claim 53
Dependent Claim
17 words
The process of claim 49, wherein the reaction temperature is from about 50° to about 125° C.
Claim 54
Dependent Claim
17 words
The process of claim 32, wherein the reaction time is from about 1 to about 150 hours.
Claim 55
Dependent Claim
17 words
The process of claim 51, wherein the reaction time is from about 3 to about 24 hours.
Claim 56
Dependent Claim
28 words
A process for the production of an acetylene terminated sulfone which comprises subjecting an hydroxy-acetylene terminated phenoxydiphenyl sulfone to base catalyzed cleavage to form said acetylene terminated sulfone.
Claim 57
Dependent Claim
28 words
A process for the production of an acetylene terminated sulfone which comprises subjecting an hydroxy-acetylene terminated phenoxydiphenyl sulfone to base catalyzed cleavage to form said acetylene terminated sulfone.
Claim 58
Dependent Claim
17 words
The process of claim 53, wherein the base used in the base catalyzed cleavage is potassium hydroxide.
Claim 59
Dependent Claim
17 words
The process of claim 53, wherein the reaction temperature is from about 70° to about 130° C.
Claim 60
Dependent Claim
17 words
The process of claim 56, wherein the reaction temperature is from about 90° to about 120° C.
Claim 61
Dependent Claim
17 words
The process of claim 53, wherein the reaction time is from about 0.5 to about 10 hours.
Claim 62
Dependent Claim
17 words
The process of claim 57, wherein the reaction time is from about 1 to about 4 hours.
Claim 63
Dependent Claim
99 words
A process for the production of an acetylene terminated sulfone which comprises: (a) reacting a sulfonyldiphenol with a material selected from the group consisting of a metadibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a sodium base to form an hydroxyphenylbromophenoxyphenyl sulfone; (b) reacting said hydroxyphenylbromophenoxyphenyl sulfone with a substituted terminal acetylene compound containing at least three carbon atoms and an hydroxy group on the carbon atom adjacent to the acetylene group to form the corresponding hydroxy-acetylene phenoxyphenylhydroxyphenyl sulfone; and (c) subjecting said hydroxy-acetylene phenoxyphenylhydroxyphenyl sulfone to base catalyzed cleavage to form the corresponding acetylene terminated sulfone.
Claim 64
Dependent Claim
99 words
A process for the production of an acetylene terminated sulfone which comprises: (a) reacting a sulfonyldiphenol with a material selected from the group consisting of a metadibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a sodium base to form an hydroxyphenylbromophenoxyphenyl sulfone; (b) reacting said hydroxyphenylbromophenoxyphenyl sulfone with a substituted terminal acetylene compound containing at least three carbon atoms and an hydroxy group on the carbon atom adjacent to the acetylene group to form the corresponding hydroxy-acetylene phenoxyphenylhydroxyphenyl sulfone; and (c) subjecting said hydroxy-acetylene phenoxyphenylhydroxyphenyl sulfone to base catalyzed cleavage to form the corresponding acetylene terminated sulfone.
Claim 65
Dependent Claim
12 words
The process of claim 59, wherein said sodium base is sodium hydroxide.
Claim 66
Dependent Claim
24 words
The process of claism 59, wherein said sulfonyldiphenol and said dibromobenzene are reacted in the presence of a catalytic amount of a copper salt.
Claim 67
Dependent Claim
24 words
The process of claism 59, wherein said sulfonyldiphenol and said dibromobenzene are reacted in the presence of a catalytic amount of a copper salt.
Claim 68
Dependent Claim
10 words
The process of claim 59, wherein said sulfonyldiphenol is 4,4'-sulfonyldiphenol.
Claim 69
Dependent Claim
15 words
The process of claim 59, wherein the dibromobenzene is a mixture of meta- and para-dibromobenzene.
Claim 70
Dependent Claim
23 words
The process of claim 61, wherein said copper salt is cuprous chloride, cuprous iodide, copper stearate, copper acetate, copper acetonylacetonate or cuprous bromide.
Claim 71
Dependent Claim
12 words
The process of claim 64, wherein said copper salt is cuprous chloride.
Claim 72
Dependent Claim
72 words
The process of claim 59, wherein said substituted terminal acetylene compound has the formula: H--C.tbd.C--Z wherein Z represents the moiety: ##STR42## wherein R 2 and R 3 can be the same or different and are selected from the group consisting of hydrogen and lower alkyl groups having from 1 to 4 carbon atoms, phenyl and substituted phenyl, and wherein R 2 and R 3 can form a saturated 5- or 6-membered ring.
Claim 73
Dependent Claim
19 words
The process of claim 66, wherein said terminal acetylene compound is 3-methylbutyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, 3-ethyl-1-pentyn-3-ol, 2-phenyl-3-butyn-2-ol, 1-ethynylcyclohexanol or 1-ethynylcyclopentanol.
Claim 74
Dependent Claim
12 words
The process of claim 67, wherein said terminal acetylene compound is 3-methyl-butyn-3-ol.
Claim 75
Dependent Claim
27 words
The process of claim 59, wherein said sulfonyldiphenol and said dibromobenzene are reacted at a temperature in the range of between about 100° and about 250° C.
Claim 76
Dependent Claim
20 words
The process of claim 69, wherein said temperature is in the range of between about 140° and about 200° C.
Claim 77
Dependent Claim
18 words
The process of claim 59 wherein said sulfonyldiphenol and dibromobenzene are reacted in the presence of a solvent.
Claim 78
Dependent Claim
18 words
The process of claim 71, wherein said solvent is tetrahydrothiophene 1,1-dioxide, dimethylsulfoxide, N-methylprolidone or bis-methoxy ethoxy diethyl ether.
Claim 79
Dependent Claim
11 words
The process of claim 72, wherein said solvent is tetrahydrothiophene 1,1-dioxide.
Claim 80
Dependent Claim
42 words
A process for the production of an hydroxyphenylbromophenoxyphenyl sulfone which comprises reacting a sulfonyldiphenol with a material selected from the group consisting of a meta-dibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a sodium base to form an hydroxyphenylbromophenoxyphenyl sulfone.
Claim 81
Dependent Claim
42 words
A process for the production of an hydroxyphenylbromophenoxyphenyl sulfone which comprises reacting a sulfonyldiphenol with a material selected from the group consisting of a meta-dibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a sodium base to form an hydroxyphenylbromophenoxyphenyl sulfone.
Claim 82
Dependent Claim
24 words
The process of claim 74, wherein said sulfonyldiphenol and said dibromobenzene are reacted in the presence of a catalytic amount of a copper salt.
Claim 83
Dependent Claim
23 words
The process of claim 74, wherein said copper salt is cuprous chloride, cuprous iodide, copper stearate, copper acetate, copper acetonylacetonate or cuprous bromide.
Claim 84
Dependent Claim
10 words
The process of claim 74, wherein said sulfonyldiphenol is 4,4'-sulfonyldiphenol.
Claim 85
Dependent Claim
15 words
The process of claim 74, wherein the dibromobenzene is a mixture of meta- and para-dibromobenzene.
Claim 86
Dependent Claim
12 words
The process of claim 74, wherein said sodium base is sodium hydroxide.
Claim 87
Dependent Claim
12 words
The process of claim 76, wherein said copper salt is cuprous chloride.
Claim 88
Dependent Claim
22 words
The process of claim 75, wherein the amount of said copper salt employed is from about 0.1 to about 10 mole percent.
Claim 89
Dependent Claim
22 words
The process of claim 81, wherein the amount of said copper salt employed is from about 1.0 to about 5.0 mole percent.
Claim 90
Dependent Claim
27 words
The process of claim 74, wherein said sulfonyldiphenol and said dibromobenzene are reacted at a temperature in the range of between about 100° and about 250° C.
Claim 91
Dependent Claim
20 words
The process of claim 83, wherein said temperature is in the range of between about 140° and about 200° C.
Claim 92
Dependent Claim
18 words
The process of claim 74, wherein said sulfonyldiphenol and dibromobenzene are reacted in the presence of a solvent.
Claim 93
Dependent Claim
18 words
The process of claim 85, wherein said solvent is tetrahydrothiophene 1,1-dioxide, dimethylsulfoxide, N-methylprolidone or bis-methoxy ethoxy diethyl ether.
Claim 94
Dependent Claim
11 words
The process of claim 84, wherein said solvent is tetrahydrothiophene 1,1-dioxide.
Claim 95
Dependent Claim
17 words
The process of claim 74, wherein the reaction time is from about 1 to about 150 hours.
Claim 96
Dependent Claim
17 words
The process of claim 88, wherein the reaction time is from about 3 to about 24 hours.
Claim 97
Dependent Claim
84 words
A process for the production of an hydroxy-acetylene terminated phenoxyphenylhydroxyphenyl sulfone which comprises reacting an hydroxyphenylbromophenoxyphenyl sulfone with a substituted terminal acetylene compound having the formula: H--C.tbd.C--Z wherein Z represents the moiety: ##STR43## wherein R 2 and R 3 can be the same or different and are selected from the group consisting of hydrogen and lower alkyl groups having from one to 4 carbon atoms, phenyl and substituted phenyl, and wherein R 2 and R 3 can form a saturated 5- or 6-membered ring.
Claim 98
Dependent Claim
84 words
A process for the production of an hydroxy-acetylene terminated phenoxyphenylhydroxyphenyl sulfone which comprises reacting an hydroxyphenylbromophenoxyphenyl sulfone with a substituted terminal acetylene compound having the formula: H--C.tbd.C--Z wherein Z represents the moiety: ##STR43## wherein R 2 and R 3 can be the same or different and are selected from the group consisting of hydrogen and lower alkyl groups having from one to 4 carbon atoms, phenyl and substituted phenyl, and wherein R 2 and R 3 can form a saturated 5- or 6-membered ring.
Claim 99
Dependent Claim
71 words
The process of claim 90, wherein a solvent is employed wherein said solvent is an amine solvent having the formula: ##STR44## wherein R 4 , R 5 and R 6 can be the same or different and are selected from the group consisting of hydrogen and lower alkyl groups having from one to 4 carbon atoms, with the proviso that no more than one of said R groups can be hydrogen.
Claim 100
Dependent Claim
20 words
The process of claim 90, wherein said substituted terminal acetylene compound is 3-methylbutyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, 3-ethyl-1-pentyn-3-ol, 2-phenyl-3-butyn-2-ol, 1-ethynylcyclohexanol or 1-ethynylcyclopentanol.
Claim 101
Dependent Claim
13 words
The process of claim 92, wherein said substituted terminal acetylene compound is 3-methylbutyn-3-ol.
Claim 102
Dependent Claim
18 words
The process of claim 91, wherein said amine solvent is dimethylamine, trimethylamine, diethylamine, triethylamine, ethylpropylamine, ethylbutylamine or dibutylamine.
Claim 103
Dependent Claim
11 words
The process of claim 94, wherein said amine solvent is triethylamine.
Claim 104
Dependent Claim
61 words
The process of claim 90, wherein a complex catalyst is employed wherein said catalyst is a palladium complex having the formula: ##STR45## where X is bromine, iodine or chlorine, and R, R' and R" are the same or different and are selected from the group consisting of phenyl, alkyl groups having from 1 to 4 carbon atoms and substituted phenyl groups.
Claim 105
Dependent Claim
33 words
The process of claim 96, wherein said palladium complex is bis(triphenylphosphine)palladium dichloride, bis(triphenylphosphine)palladium dibromide, bis(tri-n-butylphosphine)palladium dichloride, bis(tri-t-butyl-phosphine)palladium dichloride, bis(tri-i-butylphosphine)palladium dichloride, bis(triethylphosphine)palladium dichloride, bis(tripropylphosphine)palladium dichloride, bis(tritolylphosphine)palladium dichloride, bis(trianisylphosphine)palladium dichloride, bis(tri(chlorophenyl)palladium dichloride or bis(tri(bromophenyl)phosphine)palladium dichloride.
Claim 106
Dependent Claim
22 words
The process of claim 96, wherein the amount of said palladium catalyst employed is from about 0.01 to about 1.0 mole percent.
Claim 107
Dependent Claim
23 words
The process of claim 98, wherein the amount of said palladium complex catalyst employed is from about 0.02 to about 0.05 mole percent.
Claim 108
Dependent Claim
14 words
The process of claim 96, wherein a promoter comprising a copper salt is employed.
Claim 109
Dependent Claim
23 words
The process of claim 100, wherein said copper salt is cuprous chloride, cuprous iodide, copper stearate, copper acetonate, copper acetonylacetonte or cuprous bromide.
Claim 110
Dependent Claim
12 words
The process of claim 101, wherein said copper salt is cuprous chloride.
Claim 111
Dependent Claim
21 words
The process of claim 100, wherein the molar ratio of promoter to palladium complex is from about 0.5:1 to about 20:1.
Claim 112
Dependent Claim
21 words
The process of claim 103, wherein the molar ratio of promoter to palladium complex is from about 1:1 to about 5:1.
Claim 113
Dependent Claim
25 words
The process of claim 90, wherein the molar ratio of said hydroxyphenylbromophenoxyphenyl sulfone to said terminal acetylene compound is from about 1:0.5 to about 1:100.
Claim 114
Dependent Claim
25 words
The process of claim 105, wherein the molar ratio of said hydroxyphenylbromophenoxyphenyl sulfone to said terminal acetylene compound is from about 1:1 to about 1:5.
Claim 115
Dependent Claim
17 words
The process of claim 90, wherein the reaction temperature is from about 20° to about 200° C.
Claim 116
Dependent Claim
17 words
The process of claim 107, wherein the reaction temperature is from about 50° to about 125° C.
Claim 117
Dependent Claim
17 words
The process of claim 90, wherein the reaction time is from about 1 to about 150 hours.
Claim 118
Dependent Claim
17 words
The process of claim 109, wherein the reaction time is from about 3 to about 24 hours.
Claim 119
Dependent Claim
28 words
A process for the production of an hydroxyacetylene terminated sulfone which comprises subjecting an hydroxy-acetylene terminated phenoxyphenylhydroxyphenyl sulfone to base catalyzed cleavage to form said acetylene terminated sulfone.
Claim 120
Dependent Claim
28 words
A process for the production of an hydroxyacetylene terminated sulfone which comprises subjecting an hydroxy-acetylene terminated phenoxyphenylhydroxyphenyl sulfone to base catalyzed cleavage to form said acetylene terminated sulfone.
Claim 121
Dependent Claim
17 words
The process of claim 111, wherein the base used in the base catalyzed cleavage is potassium hydroxide.
Claim 122
Dependent Claim
17 words
The process of claim 111, wherein the reaction temperature is from about 70° to about 130° C.
Claim 123
Dependent Claim
17 words
The process of claim 113, wherein the reaction temperature is from about 90° to about 120° C.
Claim 124
Dependent Claim
17 words
The process of claim 111, wherein the reaction time is from about 0.5 to about 10 hours.
Claim 125
Dependent Claim
17 words
The process of claim 115, wherein the reaction time is from about 1 to about 4 hours.
Claim 126
Dependent Claim
42 words
A process for the production of bis-bromophenoxydiphenyl sulfone which comprises reacting a hydroxyphenylbromophenoxyphenyl sulfone with a material selected from the group consisting of a meta-dibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a potassium base to produce a bis-bromophenoxydiphenyl sulfone.
Claim 127
Dependent Claim
42 words
A process for the production of bis-bromophenoxydiphenyl sulfone which comprises reacting a hydroxyphenylbromophenoxyphenyl sulfone with a material selected from the group consisting of a meta-dibromobenzene, a para-dibromobenzene and mixtures thereof in the presence of a potassium base to produce a bis-bromophenoxydiphenyl sulfone.
Claim 128
Dependent Claim
12 words
The process of claim 117, wherein said potassium base is potassium hydroxide.
Claim 129
Dependent Claim
13 words
The process of claim 117, wherein said hydroxyphenylbromophenoxyphenyl sulfone is reacted with para-dibromobenzene.
Claim 130
Dependent Claim
12 words
The process of claim 117, wherein said hydroxyphenylbromophenoxyphenyl sulfone is 4-hydroxy-4'-(3-bromophenoxy)diphenyl sulfone.
Claim 131
Dependent Claim
12 words
The process of claim 119, wherein said hydroxyphenylbromophenoxyphneyl sulfone is 4-hydroxy-4'-(3-bromophenoxy)diphenyl sulfone.
Claim 132
Dependent Claim
25 words
The process of claim 117, wherein said hydroxyphenylbromophenoxyphenyl sulfone and said dibromobenzene are reacted in the presence of a catalytic amount of a copper salt.
Claim 133
Dependent Claim
23 words
The process of claim 122, wherein said copper salt is cuprous chloride, cuprous iodide, copper stearate, copper acetonate, copper acetonylacetonate or cuprous bromide.
Claim 134
Dependent Claim
12 words
The process of claim 123, wherein said copper salt is cuprous chloride.
Claim 135
Dependent Claim
22 words
The process of claim 124, wherein the amount of said copper salt employed is from about 0.1 to about 10 mole percent.
Claim 136
Dependent Claim
22 words
The process of claim 125, wherein the amount of said copper salt employed is from about 1.0 to about 5.0 mole percent.
Claim 137
Dependent Claim
28 words
The process of claim 117, wherein said hydroxyphenylbromophenoxyphenyl sulfone and said dibromobenzene are reacted at a temperature in the range of between about 100° to about 250° C.
Claim 138
Dependent Claim
19 words
The process of claim 127, wherein said temperature is in the range of between about 140° and 200° C.
Claim 139
Dependent Claim
20 words
The process of claim 117, wherein said hydroxyphenylbromophenoxyphenyl sulfone and said dibromobenzene are reacted in the presence of a solvent.
Claim 140
Dependent Claim
18 words
The process of claim 129, wherein said solvent is tetrahydrothiophene 1,1-dioxide, dimethylsulfoxide, N-methylprolidone or bis-methoxy ethoxy diethyl ether.
Claim 141
Dependent Claim
11 words
The process of claim 130, wherein said solvent is tetrahydrothiophene 1,1-dioxide.
Claim 142
Dependent Claim
17 words
The process of claim 117, wherein the reaction time is from about 1 to about 150 hours.
Claim 143
Dependent Claim
17 words
The process of claim 132, wherein the reaction time is from about 3 to about 24 hours.
Claim 144
Dependent Claim
49 words
A process for the production of an oligomeric bromophenoxydiphenyl sulfone, which comprises reacting an hydroxyphenylbromophenoxyphenyl sulfone with a bromophenoxydiphenyl sulfone, wherein each of said compounds contain the bromine and oxygen moieties attached directly to the phenyl nucleus in a meta or para configuration to form an oligomeric bromophenoxydiphenyl sulfone.
Claim 145
Dependent Claim
49 words
A process for the production of an oligomeric bromophenoxydiphenyl sulfone, which comprises reacting an hydroxyphenylbromophenoxyphenyl sulfone with a bromophenoxydiphenyl sulfone, wherein each of said compounds contain the bromine and oxygen moieties attached directly to the phenyl nucleus in a meta or para configuration to form an oligomeric bromophenoxydiphenyl sulfone.
Claim 146
Dependent Claim
44 words
The process of claim 134, wherein said oligomeric bromophenoxydiphenyl sulfone is reacted with a substituted terminal acetylene compound containing at least three carbon atoms and an hydroxy group on the carbon atom adjacent the acetylene group to form the corresponding oligomeric hydroxy-acetylene terminated sulfones.
Claim 147
Dependent Claim
12 words
The process of claim 134, wherein the hydroxyphenylbromophenoxyphenyl sulfone is 4-hydroxy-4'-(3-bromophenoxy)diphenyl sulfone.
Claim 148
Dependent Claim
12 words
The process of claim 134, wherein the bis-bromophenoxydiphenyl sulfone is 4,4'-bis-(3-bromophenoxy)diphenyl sulfone.
Claim 149
Dependent Claim
83 words
The process of claim 135, wherein the substituted terminal acetylene compound has the formula: H--C.tbd.C--Z wherein Z represents the moiety: ##STR46## wherein R 2 and R 3 can be the same or different and are selected from the group consisting of hydrogen and lower alkyl groups having from 1 to 4 carbon atoms, phenyl and substituted phenyl, and wherein R 2 and R 3 when taken together with the carbon atom to which they are attached form a saturated 5- or 6-membered ring.
Claim 150
Dependent Claim
14 words
The process of claim 138, wherein R 2 and R 3 are each methyl.
Claim 151
Dependent Claim
17 words
The process of claim 135, wherein the base employed in the base catalyzed cleavage is potassium hydroxide.
Claim 152
Dependent Claim
22 words
The process of claim 135, wherein the temperature of the reaction is in the range from about 70° to about 130° C.
Claim 153
Dependent Claim
22 words
The process of claim 141, wherein the temperature of the reaction is in the range from about 90° to about 120° C.
Claim 154
Dependent Claim
17 words
The process of claim 135, wherein the reaction time is from about 0.5 to about 10 hours.
Claim 155
Dependent Claim
17 words
The process of claim 143, wherein the reaction time is from about 1 to about 4 hours.
Claim 156
Dependent Claim
25 words
The process of claim 135, wherein said oligomeric hydroxy-acetylene terminated sulfones are subjected to base catalyzed cleavage to form the corresponding oligomeric acetylene terminated sulfones.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-10-25 | 1986-04-26 | 1986-10-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-10-25 | 1990-04-26 | 1990-10-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-10-25 | 1994-04-26 | 1994-10-26 | $7700.00 | Window Closed / Lapsed |