Patent US3825808A successfully refreshed from Google Patents.
US4136117A
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Preparation of 2,6-dinitroanilines
Assignee: Wyeth Holdings LLC
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Filing: 1977-03-14
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Granted: 1979-01-23
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Expires: 1997-03-14
Abstract
Abstract This invention relates to a novel process for the preparation of N-alkylated and N,N-dialkylated 2,6-dinitroaniline herbicidal agents.
Inventors
- 👤 Robert E. Diehl
- 👤 Stephen D. Levy
- 👤 William H. Gastrock
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 03:50
CPC Classifications
C; C07; C07C; C07C209/00; C07C209/68; C07C209/76; C07C201/00; C07C201/06; C07C201/08; C07C211/00; C07C211/43; C07C211/44; C07C211/52
Claims Analysis
Total Claims: 19
Claim 1
Independent Claim
325 words
A method for the manufacture of a compound of the formula: ##STR18## wherein Y is alkyl C 1 -C 4 , halogen or CF 3 ; Z is hydrogen, halogen, alkyl C 1 -C 4 , alkoxy C 1 -C 4 , monohaloalkyl C 1 -C 4 , or monoalkoxy (C 1 -C 4 ) alkyl (C 1 -C 4 ); R 1 represents alkyl C 1 -C 6 , cycloalkyl C 4 -C 6 , monohaloalkyl C 1 -C 4 or alkoxyalkyl where the alkyl group is C 1 -C 4 and the alkoxy group is C 1 -C 4 ; R 2 is hydrogen or one of the groups of R 1 ; comprising reacting an N-alkylated aniline of the formula: ##STR19## wherein R 1 , R 2 , Y and Z are as defined above and W and V are hydrogen or nitro provided W and V are not both nitro; with a three-component nitrating agent having a composition with the following limits: 60% HNO 3 , 8% H 2 SO 4 , 32% H 2 O; 50% HNO 3 , 35% H 2 SO 4 , 15% H 2 O; 2% HNO 3 , 68% H 2 SO 4 , 30% H 2 O; 2% HNO 3 , 20% H 2 SO 4 , 78% H 2 O; at a temperature in the range of from 0° C. to 70° C.; further characterized in that, when W and V are hydrogen in the N-alkylated aniline, from 2.2 to 5.0 moles of nitric acid are employed per mole of the N-alkylated aniline and, when one of W and V in the N-alkylated aniline is nitro, the moles of nitric acid per mole of N-alkylated aniline is in the range of 1.2 to 4.0 moles and when a compound of the formula: ##STR20## wherein R 1 Y and Z are as defined above is formed in the reaction mixture denitrosating the reaction mixture.
Claim 2
Independent Claim
325 words
A method for the manufacture of a compound of the formula: ##STR18## wherein Y is alkyl C 1 -C 4 , halogen or CF 3 ; Z is hydrogen, halogen, alkyl C 1 -C 4 , alkoxy C 1 -C 4 , monohaloalkyl C 1 -C 4 , or monoalkoxy (C 1 -C 4 ) alkyl (C 1 -C 4 ); R 1 represents alkyl C 1 -C 6 , cycloalkyl C 4 -C 6 , monohaloalkyl C 1 -C 4 or alkoxyalkyl where the alkyl group is C 1 -C 4 and the alkoxy group is C 1 -C 4 ; R 2 is hydrogen or one of the groups of R 1 ; comprising reacting an N-alkylated aniline of the formula: ##STR19## wherein R 1 , R 2 , Y and Z are as defined above and W and V are hydrogen or nitro provided W and V are not both nitro; with a three-component nitrating agent having a composition with the following limits: 60% HNO 3 , 8% H 2 SO 4 , 32% H 2 O; 50% HNO 3 , 35% H 2 SO 4 , 15% H 2 O; 2% HNO 3 , 68% H 2 SO 4 , 30% H 2 O; 2% HNO 3 , 20% H 2 SO 4 , 78% H 2 O; at a temperature in the range of from 0° C. to 70° C.; further characterized in that, when W and V are hydrogen in the N-alkylated aniline, from 2.2 to 5.0 moles of nitric acid are employed per mole of the N-alkylated aniline and, when one of W and V in the N-alkylated aniline is nitro, the moles of nitric acid per mole of N-alkylated aniline is in the range of 1.2 to 4.0 moles and when a compound of the formula: ##STR20## wherein R 1 Y and Z are as defined above is formed in the reaction mixture denitrosating the reaction mixture.
Claim 3
Dependent Claim
73 words
A method according to claim 1 wherein the nitrating reagent is a composition within the limits of 45% HNO 3 , 19% H 2 SO 4 , 36% H 2 O; 45% HNO 3 , 36% H 2 SO 4 , 19% H 2 O: 20% HNO 3 , 52% H 2 SO 4 , 28% H 2 O; 20% HNO 3 , 27% H 2 SO 4 , 53% H 2 O.
Claim 4
Dependent Claim
22 words
A method according to claim 1 wherein the temperature is in the range of from about 35° C. to about 60° C.
Claim 5
Dependent Claim
12 words
A method according to claim 1 wherein the N-alkylated aniline is N-(1-ethylpropyl)-3,4-dimethylaniline.
Claim 6
Dependent Claim
12 words
A method according to claim 1 wherein the N-alkylated aniline is N-(2-butyl)-3,4-dimethylaniline.
Claim 7
Dependent Claim
48 words
A method according to claim 1 wherein R 2 is hydrogen further characterized by the step of denitrosating the reaction mixture formed therein by reacting the reaction mixture with 1 mole of concentrated hydrochloric acid and 1 mole of sulfamic acid per mole of any N-nitroso compound present.
Claim 8
Dependent Claim
21 words
A method according to claim 6 wherein the mole ratio of hydrochloric acid to N-nitroso compound is between 5:1 and 3:1.
Claim 9
Dependent Claim
29 words
A method according to claim 1 wherein the mole ratio of sulfamic acid present in the reaction mixture to the N-nitroso compound present in the reaction mixture is 2:1.
Claim 10
Dependent Claim
36 words
A method according to claim 1 wherein W and V are hydrogen in the N-alkylated aniline and a range of from 2.5 to 3.5 moles of nitric acid are employed per mole of said N-alkylated aniline.
Claim 11
Dependent Claim
35 words
A method according to claim 1 wherein W or V in the N-alkylated aniline is nitro and the moles of nitric acid per mole of N-alkylated aniline is in the range of 1.5 to 2.5.
Claim 12
Dependent Claim
25 words
A method according to claim 1 wherein the mole ratio of sulfuric acid to N-alkylated aniline is in the range of from 1.5:1 to 15.0:1.
Claim 13
Dependent Claim
14 words
A method according to claim 10 wherein the range is from 2.0:1 to 10.0:1.
Claim 14
Dependent Claim
159 words
A method for the nitration of N-(1-ethylpropyl)-3,4-dimethylaniline according to claim 1 wherein the nitrating agent has a water content from about 35% to 53% by weight and the aniline compound is reacted in an amount to give a mole ratio of nitric acid to said aniline of about 3.25:1 and a mole ratio of sulfuric acid to said aniline compound of about 2.25:1, maintaining the temperature of the reaction mixture from about 35° C. to 70° C. while the reactants are mixed therein over a period of about 2 hours, maintaining the temperature of said reaction mixture from about 35° C. to about 70° C. for about 1 hour on completion of said mixing, separating the spent acid from the organic mixture, adding a denitrosating mixture of hydrochloric acid and sulfamic acid to the organic mixture, maintaining a temperature of 70° C. to 100° C. over a period of 1 to 6 hours and recovering the N-(1-ethylpropyl)-2,6-dinitro-3,4-dimethylaniline product therefrom.
Claim 15
Dependent Claim
38 words
A method according to claim 13 wherein the nitration is conducted in an ethylene dichloride solvent, further characterized in that the solvent ratio expressed in milliliters of ethylenedichloride per gram of N-(1-ethylpropyl)-3,4-dimethylaniline ranges from about 3.0:1.0 to 0.5:1.0.
Claim 16
Dependent Claim
14 words
A method according to claim 14 wherein the solvent ratio is from about 0.75:1.0.
Claim 17
Dependent Claim
160 words
A method for the nitration of N-(2-butyl)-3,4-dimethylaniline according to claim 1 wherein the nitrating agent has a water content from about 40% to 53% by weight, wherein said aniline compound is reacted in an amount to give a mole ratio of nitric acid to said aniline compound of about 3.25:1 and a mole ratio of sulfuric acid to said aniline compound of about 2.25:1, maintaining the temperature of the reaction mixture from about 50° C. to 70° C. while the reactants are mixed therein over a period of about 2 hours, maintaining the temperature of said reaction mixture from about 50° C. to about 70° C. for about 1 hour on completion of said mixing, separating the spent acid from the organic mixture, adding a denitrosating mixture of hydrochloric acid and sulfamic acid to the organic mixture, maintaining a temperature of 70° C. to 100° C. over a period of 1 to 6 hours and recovering the N-(2-butyl)-2,6-dinitro-3,4-dimethylaniline product therefrom.
Claim 18
Dependent Claim
40 words
A method according to claim 16 wherein the nitration is conducted in an ethylene dichloride solvent, further characterized in that the solvent ratio expressed in milliliters of ethylene dichloride per gram of N-(2-butyl)-3,4-dimethylaniline ranges from about 3.0:1.0 to about 0.5:1.0.
Claim 19
Dependent Claim
14 words
A method according to claim 17 wherein the solvent ratio is from about 0.75:1.0.
References Cited (Backward Citations)
US3654363A
Cited
US3927127A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-01-22 | 1982-07-24 | 1983-01-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-01-22 | 1986-07-24 | 1987-01-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-01-22 | 1990-07-24 | 1991-01-23 | $7700.00 | Window Closed / Lapsed |