US4172098A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Manufacture of substituted halobenzenes
Assignee: BASF SE
•
Filing: 1977-11-15
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Granted: 1979-10-23
•
Expires: 1997-11-15
Abstract
Abstract Halobenzenes are manufactured by (a) a one-vessel reaction of anilines with halogenating agents to give haloanilines, followed by reaction of the mixture thus obtained with alkanols and nitrosylating agents in the presence of water and acid at not less than 35° C. or (b) the corresponding reaction of a haloaniline which has been manufactured in the above manner or by some other method and has been isolated from its reaction mixture. The products are starting materials for the manufacture of drugs, dyes and pesticides.
Inventors
- 👤 Horst Scheuermann
- 👤 Ulrich Jersak
- 👤 Helmut Gorth
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 15:42
CPC Classifications
C; C07; C07C; C07C201/00; C07C201/06; C07C201/12; C07C51/00; C07C51/347; C07C51/363; C07C51/377
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
105 words
A process for the manufacture of halobenzenes of the formula ##STR25## where R 1 and R 4 may be identical or different and each is halogen, R 3 is --COOR 5 and R 4 may also be hydrogen or nitro, and R 5 is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical, wherein a haloaminobenzoic acid compound of the formula ##STR26## where R 1 , R 5 and R 4 have the above meanings, is reacted with an aliphatic, cycloaliphatic or araliphatic alcohol and a nitrosylating agent in the presence of an acid at not less than 35° C., in the presence of water.
Claim 2
Dependent Claim
105 words
A process for the manufacture of halobenzenes of the formula ##STR25## where R 1 and R 4 may be identical or different and each is halogen, R 3 is --COOR 5 and R 4 may also be hydrogen or nitro, and R 5 is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical, wherein a haloaminobenzoic acid compound of the formula ##STR26## where R 1 , R 5 and R 4 have the above meanings, is reacted with an aliphatic, cycloaliphatic or araliphatic alcohol and a nitrosylating agent in the presence of an acid at not less than 35° C., in the presence of water.
Claim 3
Dependent Claim
28 words
A process as claimed in claim 1, in which the reaction is carried out with from 3 to 30 equivalents of alcohol per mole of starting material III.
Claim 4
Dependent Claim
35 words
A process as claimed in claim 1, in which the reaction is carried out with from 1.1 to 5 moles of alkyl nitrite, nitrous acid ester and/or nitrous fumes per mole of starting material III.
Claim 5
Dependent Claim
29 words
A process as claimed in claim 1, in which the reaction is carried out with from 1.1 to 5 moles of monoglycol ester per mole of starting material III.
Claim 6
Dependent Claim
29 words
A process as claimed in claim 1, in which the reaction is carried out with from 0.55 to 2.5 moles of diglycol ester per mole of starting material III.
Claim 7
Dependent Claim
33 words
A process as claimed in claim 1, in which the reaction is carried out with addition of water in an amount of from 0.2 to 10,000 moles per mole of starting material III.
Claim 8
Dependent Claim
27 words
A process as claimed in claim 1, in which the reaction is carried out with from 1.5 to 15 equivalents of acid, based on starting material III.
Claim 9
Dependent Claim
25 words
A process as claimed in claim 1, in which the reaction is carried out at from 35° C. to the boiling point of the mixture.
Claim 10
Dependent Claim
31 words
A process as claimed in claim 1, in which the second step of the reaction is carried out with from 1.5 to 15 equivalents of acid, based on starting material III.
Claim 11
Dependent Claim
124 words
A process for the manufacture of halonitrobenzenes of the formula ##STR27## where R 1 and R 4 may be identical or different and each is halogen, and R 4 may also be hydrogen, wherein, in a first step, a nitroaniline of the formula ##STR28## where R 4 has the above meaning, is reacted with a halogenating agent in the presence of water and an acid, and the halonitroaniline thus obtained, of the formula ##STR29## where R 1 and R 4 have the above meanings, is reacted in a second step, without isolation from its reaction mixture, with an aliphatic, cycloaliphatic or araliphatic alcohol and a nitrosylating agent in the presence of an acid at not less than 35° C., in the presence of water.
Claim 12
Dependent Claim
124 words
A process for the manufacture of halonitrobenzenes of the formula ##STR27## where R 1 and R 4 may be identical or different and each is halogen, and R 4 may also be hydrogen, wherein, in a first step, a nitroaniline of the formula ##STR28## where R 4 has the above meaning, is reacted with a halogenating agent in the presence of water and an acid, and the halonitroaniline thus obtained, of the formula ##STR29## where R 1 and R 4 have the above meanings, is reacted in a second step, without isolation from its reaction mixture, with an aliphatic, cycloaliphatic or araliphatic alcohol and a nitrosylating agent in the presence of an acid at not less than 35° C., in the presence of water.
Claim 13
Dependent Claim
90 words
A process for the manufacture of halobenzoic acid compounds of the formula ##STR30## where R 1 is halogen, R 4 is hydrogen, halogen or nitro and R 5 is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical, wherein a haloaminobenzoic acid compound of the formula ##STR31## where R 1 , R 5 and R 4 have the above meanings, is reacted with an aliphatic, cycloaliphatic or araliphatic alcohol and a nitrosylating agent in the presence of an acid at not less than 35° C., in the presence of water.
Claim 14
Dependent Claim
90 words
A process for the manufacture of halobenzoic acid compounds of the formula ##STR30## where R 1 is halogen, R 4 is hydrogen, halogen or nitro and R 5 is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical, wherein a haloaminobenzoic acid compound of the formula ##STR31## where R 1 , R 5 and R 4 have the above meanings, is reacted with an aliphatic, cycloaliphatic or araliphatic alcohol and a nitrosylating agent in the presence of an acid at not less than 35° C., in the presence of water.
Claim 15
Dependent Claim
162 words
A process for the manufacture of halobenzenes of the formula ##STR32## where R 1 and R 4 may be identical or different and each is halogen, R 3 is nitro or --COOR 5 and R 4 may also be hydrogen or, if R 3 is --COOR 5 , may also be nitro, and R 5 is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical, wherein an aniline of the formula ##STR33## where R 3 and R 4 have the above meanings, is reacted in a first step with a halogenating agent in the presence of water and an acid, and the haloaniline thus formed, of the formula ##STR34## where R 1 , R 3 and R 4 have the above meanings, is reacted in a second step, without isolation from its reaction mixture, with an aliphatic, cycloaliphatic or araliphatic alcohol and a nitrosylating agent in the presence of an acid, at not less than 35° C., in the presence of water.
Claim 16
Dependent Claim
162 words
A process for the manufacture of halobenzenes of the formula ##STR32## where R 1 and R 4 may be identical or different and each is halogen, R 3 is nitro or --COOR 5 and R 4 may also be hydrogen or, if R 3 is --COOR 5 , may also be nitro, and R 5 is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical, wherein an aniline of the formula ##STR33## where R 3 and R 4 have the above meanings, is reacted in a first step with a halogenating agent in the presence of water and an acid, and the haloaniline thus formed, of the formula ##STR34## where R 1 , R 3 and R 4 have the above meanings, is reacted in a second step, without isolation from its reaction mixture, with an aliphatic, cycloaliphatic or araliphatic alcohol and a nitrosylating agent in the presence of an acid, at not less than 35° C., in the presence of water.
Claim 17
Dependent Claim
43 words
A process as claimed in claim 12, wherein the first step of the reaction is carried out with a ratio of from 1.0 to 5.0 moles of halogen or from 1.0 to 5.0 equivalents of halogenating agent per mole of starting material III.
Claim 18
Dependent Claim
43 words
A process as claimed in claim 12, wherein the first step of the reaction is carried out with an oxidizing agent and a hydrogen halide, in a ratio of from 1.0 to 5.0 moles of oxidizing agent per mole of starting material III.
Claim 19
Dependent Claim
39 words
A process as claimed in claim 12, in which the first step of the reaction is carried out with hydrogen peroxide as the oxidizing agent in an amount of from 1.0 to 5.0 equivalents based on starting material III.
Claim 20
Dependent Claim
35 words
A process as claimed in claim 12, in which the first step of the reaction is carried out with an amount of from 1 to 1.2 equivalents of hypochlorite per mole of starting material III.
Claim 21
Dependent Claim
39 words
A process as claimed in claim 12, in which the first step of the reaction is carried out with from 50 to 5,000 per cent by weight of water, based on the amount by weight of starting material III.
Claim 22
Dependent Claim
22 words
A process as claimed in claim 12, in which the first step of the reaction is carried out at above 25° C.
Claim 23
Dependent Claim
24 words
A process as claimed in claim 12, in which the first step of the reaction is carried out at from 27° to 100° C.
Claim 24
Dependent Claim
63 words
A process as claimed in claim 12, in which the first step of the reaction is carried out with an organic or inorganic acid which is inert under the reaction conditions and has an acid exponent (pKa) of from -7 to +2.16, in an amount of from 1 to 30 parts by weight of acid per part by weight of starting material III.
Claim 25
Dependent Claim
32 words
A process as claimed in claim 12, in which the second step of the reaction is carried out with from 3 to 30 equivalents of alcohol per mole of starting material III.
Claim 26
Dependent Claim
39 words
A process as claimed in claim 12, in which the second step of the reaction is carried out with from 1.1 to 5 moles of alkyl nitrite, nitrous acid ester and/or nitrous fumes per mole of starting material III.
Claim 27
Dependent Claim
33 words
A process as claimed in claim 12, in which the second step of the reaction is carried out with from 1.1 to 5 moles of monoglycol ester per mole of starting material III.
Claim 28
Dependent Claim
33 words
A process as claimed in claim 12, in which the second step of the reaction is carried out with from 0.55 to 2.5 moles of diglycol ester per mole of starting material III.
Claim 29
Dependent Claim
37 words
A process as claimed in claim 12, in which the second step of the reaction is carried out with addition of water in an amount of from 0.2 to 10,000 moles per mole of starting material III.
Claim 30
Dependent Claim
29 words
A process as claimed in claim 12, in which the second step of the reaction is carried out at from 35° C. to the boiling point of the mixture.
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) | 1982-10-22 | 1983-04-23 | 1983-10-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-10-22 | 1987-04-23 | 1987-10-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-10-22 | 1991-04-23 | 1991-10-23 | $7700.00 | Window Closed / Lapsed |