US4096196A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Diazotization-fluorination in a medium of hydrogen fluoride containing tertiary amine compounds
Assignee: Olin Corp
•
Filing: 1976-08-12
•
Granted: 1978-06-20
•
Expires: 1996-08-12
Abstract
Abstract Process for preparing fluoroaromatic or fluoropyridines by diazotization-fluorination of aromatic or heterocyclic amines in a solution of hydrogen fluoride containing selected tertiary amine compounds.
Inventors
- 👤 Max M. Boudakian
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 06:16
CPC Classifications
C; C07; C07C; C07C17/00; C07C17/093
Claims Analysis
Total Claims: 26
Claim 1
Independent Claim
167 words
In a process for preparing a fluorobenzene or a fluoropyridine by (1) diazotizing a corresponding aminobenzene or aminopyridine substrate in the presence of hydrogen fluoride and a diazotization agent selected from the group consisting of sodium nitrite, potassium nitrite, nitrous anhydride, nitrous acid, a nitrosyl halide, and a complex of a nitrosyl halide with hydrogen fluoride to produce a corresponding diazonium fluoride and (2) decomposing said diazonium fluoride; wherein said aminobenzene and aminopyridine substrates have either formula (I) or (II): ##STR9## wherein R' is a ring substituent selected from the group consisting of halogen; alkyl; nitro; carboxyl; hydroxy; alkoxy; and combinations thereof; m is an integer having a value of 0-3; and n is an integer having a value of 1-2, the improvement which comprises: conducting said diazotization and decomposition steps in a solution of hydrogen fluoride containing tertiary amine compounds selected from the group consisting of unsaturated heterocyclic tertiary amines, aromatic tertiary amines, alkyl tertiary amines, saturated heterocyclic amines, nitriles, tertiary amine oxides and combinations thereof.
Claim 2
Dependent Claim
167 words
In a process for preparing a fluorobenzene or a fluoropyridine by (1) diazotizing a corresponding aminobenzene or aminopyridine substrate in the presence of hydrogen fluoride and a diazotization agent selected from the group consisting of sodium nitrite, potassium nitrite, nitrous anhydride, nitrous acid, a nitrosyl halide, and a complex of a nitrosyl halide with hydrogen fluoride to produce a corresponding diazonium fluoride and (2) decomposing said diazonium fluoride; wherein said aminobenzene and aminopyridine substrates have either formula (I) or (II): ##STR9## wherein R' is a ring substituent selected from the group consisting of halogen; alkyl; nitro; carboxyl; hydroxy; alkoxy; and combinations thereof; m is an integer having a value of 0-3; and n is an integer having a value of 1-2, the improvement which comprises: conducting said diazotization and decomposition steps in a solution of hydrogen fluoride containing tertiary amine compounds selected from the group consisting of unsaturated heterocyclic tertiary amines, aromatic tertiary amines, alkyl tertiary amines, saturated heterocyclic amines, nitriles, tertiary amine oxides and combinations thereof.
Claim 3
Dependent Claim
91 words
The process of claim 1 wherein said tertiary amine compound is an unsaturated heterocyclic tertiary amine having a nucleus of 6-10 ring atoms consisting of carbon and 1 or 2 atoms of nitrogen and substituted derivatives thereof having the formula R m -X wherein X represents said nucleus, wherein R is a carbon substituted substituent on said nucleus selected from the group consisting of lower alkyl, halogen, hydroxy loweralkyl, halo loweralkyl, lower alkoxy and ##STR10## wherein R' is lower alkyl, and wherein m is an integer having a value of 0-3.
Claim 4
Dependent Claim
54 words
The process of claim 2 wherein said tertiary amine has the formula: ##STR11## wherein each R is a carbon substituted substituent selected from the group consisting of lower alkyl, halogen, hydroxy loweralkyl, halo loweralkyl, lower alkoxy and ##STR12## wherein R' is lower alkyl and wherein m is an integer having a value of 0-3.
Claim 5
Dependent Claim
11 words
The process of claim 3 wherein said tertiary amine is pyridine.
Claim 6
Dependent Claim
24 words
The process of claim 2 wherein said nucleus is selected from the group consisting of 3-picoline, 4-picoline, quinoline, isoquinoline, pyrazine, indole, pyrrole and acridine.
Claim 7
Dependent Claim
163 words
In a process for preparing a fluorobenzene or a fluoropyridine by (1) diazotizing a corresponding aminobenzene or aminopyridine substrate in the presence of hydrogen fluoride and a diazotization agent selected from the group consisting of sodium nitrite, potassium nitrite, nitrous anhydride, nitrous acid, a nitrosyl halide, and a complex of a nitrosyl halide with hydrogen fluoride, to produce a corresponding diazonium fluoride and (2) decomposing said diazonium fluoride; wherein said aminobenzene and aminopyridine substrates have either formula (I) or (II): ##STR13## wherein R' is a ring substituent selected from the group consisting of halogen; alkyl; nitro; carboxyl; hydroxy; alkoxy; and combinations therefor; m is an integer having a value of 0-3; and n is an integer having a value of 1-2, the improvement which comprises: conducting said diazotization and decomposition steps in a solution of hydrogen fluoride containing tertiary amine compounds selected from the group consisting of aromatic tertiary amines, alkyl tertiary amines, saturated heterocyclic amines, nitriles, tertiary amine oxides and combinations thereof.
Claim 8
Dependent Claim
163 words
In a process for preparing a fluorobenzene or a fluoropyridine by (1) diazotizing a corresponding aminobenzene or aminopyridine substrate in the presence of hydrogen fluoride and a diazotization agent selected from the group consisting of sodium nitrite, potassium nitrite, nitrous anhydride, nitrous acid, a nitrosyl halide, and a complex of a nitrosyl halide with hydrogen fluoride, to produce a corresponding diazonium fluoride and (2) decomposing said diazonium fluoride; wherein said aminobenzene and aminopyridine substrates have either formula (I) or (II): ##STR13## wherein R' is a ring substituent selected from the group consisting of halogen; alkyl; nitro; carboxyl; hydroxy; alkoxy; and combinations therefor; m is an integer having a value of 0-3; and n is an integer having a value of 1-2, the improvement which comprises: conducting said diazotization and decomposition steps in a solution of hydrogen fluoride containing tertiary amine compounds selected from the group consisting of aromatic tertiary amines, alkyl tertiary amines, saturated heterocyclic amines, nitriles, tertiary amine oxides and combinations thereof.
Claim 9
Dependent Claim
87 words
The process of claim 6 wherein said tertiary amine is an aromatic tertiary amine having the formula: ##STR14## wherein R 1 and R 2 are each selected from the group consisting of lower alkyl, hydroxy loweralkyl and phenyl, wherein R is selected from the group consisting of lower alkyl, halogen, hydroxy loweralkyl, halo loweralkyl, lower alkoxy and ##STR15## wherein R' is lower alkyl, wherein m is an integer having a value in the range of 0-3 and wherein x is an integer having a value of 0-4.
Claim 10
Dependent Claim
32 words
The process of claim 7 wherein said tertiary amine is an N,N-disubstituted aniline having the formula: ##STR16## wherein R m , R 1 and R 2 are as defined in claim 7.
Claim 11
Dependent Claim
56 words
The process of claim 6 wherein said tertiary amine is an alkyl tertiary amine or amide having the formula: ##STR17## wherein each R is independently selected from the group consisting of alkyl having 1-12 carbon atoms and hydroxy loweralkyl and wherein one of said R groups may be ##STR18## wherein R' is lower alkyl or hydrogen.
Claim 12
Dependent Claim
12 words
The process of claim 9 wherein said tertiary amine is a trialkylamine.
Claim 13
Dependent Claim
29 words
The process of claim 6 wherein said tertiary amine is a saturated heterocyclic amine having about 5-10 nuclear carbon atoms consisting of carbon and 1 or 2 nitrogen atoms.
Claim 14
Dependent Claim
29 words
The process of claim 11 wherein at least one of said nitrogen atoms is substituted with a substituent selected from the group consisting of lower alkyl and hydroxy loweralkyl.
Claim 15
Dependent Claim
11 words
The process of claim 12 wherein said tertiary amine is N-methyl-2-pyrrolidone.
Claim 16
Dependent Claim
21 words
The process of claim 6 wherein said tertiary amine is a nitrile having the formula RC.tbd.N wherein R is an alkyl.
Claim 17
Dependent Claim
10 words
The process of claim 14 wherein said nitrile is acetonitrile.
Claim 18
Dependent Claim
63 words
The process of claim 6 wherein said tertiary amine compound is a tertiary amine oxide having the formula: R.sub.1 R.sub.2 R.sub.3 --N→O wherein R 1 , R 2 and R 3 are independently selected from the group consisting of alkyl, hydroxy loweralkyl, phenyl, the carbon portion of an unsaturated heterocyclic ring having a nucleus of about 6-12 ring atoms and substituted derivatives thereof.
Claim 19
Dependent Claim
12 words
The process of claim 16 wherein said tertiary amine oxide is pyridine-N-oxide.
Claim 20
Dependent Claim
27 words
The process of claim 6 wherein said tertiary amine compounds are employed in amounts ranging from about 0.025 to about 0.5 moles per mole of hydrogen fluoride.
Claim 21
Dependent Claim
32 words
The process of claim 18 wherein said solution of hydrogen fluoride is present in a range from about 2 moles to about 30 moles per mole of said aminobenzene or aminopyridine substrate.
Claim 22
Dependent Claim
18 words
The process of claim 19 wherein said diazotization and said decomposition steps are carried out in separate steps.
Claim 23
Dependent Claim
14 words
The process of claim 19 wherein said diazotization and said decomposition steps occur simultaneously.
Claim 24
Dependent Claim
58 words
The process of claim 19 wherein said diazotization and decomposition steps are conducted in a solution of hydrogen fluoride containing from about 0.05 to about 0.25 moles of tertiary amine ion per mole of hydrogen fluoride, and from about 7.5 to about 25 moles of hydrogen fluoride are present per one mole of said aminobenzene or aminopyridine present.
Claim 25
Dependent Claim
19 words
The process of claim 22 wherein o-fluorotoluene is produced by diazotizing o-toluidine with sodium nitrite and anhydrous hydrogen fluoride.
Claim 26
Dependent Claim
15 words
The process of claim 23 wherein said diazotization and decomposition steps occur in separate steps.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-06-19 | 1981-12-19 | 1982-06-20 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-06-19 | 1985-12-19 | 1986-06-20 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-06-19 | 1989-12-19 | 1990-06-20 | $7700.00 | Window Closed / Lapsed |