US4070366A
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Alkylation process
Assignee: National Research Council Canada
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Filing: 1975-07-21
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Granted: 1978-01-24
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Expires: 1995-07-21
Abstract
Abstract Substituted pyrrole compounds, such as 3-ethyl-4-methyl-5-carbethoxy pyrrole, 2,4-dimethyl-3-acetyl pyrrole and 2-methyl-5-carboxy pyrrole-4-propionic acid diethyl ester, are alkylated in a single step by reaction with an aldehyde or ketone in the presence of both an acid condensing agent such as hydriodic acid and a compatible reducing agent such as metallic zinc or stannous chloride. Suitable carbonyl reactants include formaldehyde, paraldehyde, isobutyraldehyde, acetone, cyclohexanone and methyl-isobutyl ketone.
Inventors
- 👤 Basil V. Gregorovich
- 👤 Stewart F. MacDonald
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 10:31
CPC Classifications
C; C07; C07D; C07D207/00; C07D207/02; C07D207/30; C07D207/32; C07B; C07B37/00; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/582
Claims Analysis
Total Claims: 9
Claim 1
Independent Claim
258 words
A single step method of ring alkylating a substituted pyrrole compound which comprises the steps of reacting in a liquid system (1) a substituted pyrrole compound selected from the group consisting of 2,4-dimethyl-5-carbethoxy pyrrole, 2,4-dimethyl-3,5-dicarbethoxy pyrrole, 2-methyl-3-carbethoxy pyrrole, 2,4-dimethyl-3-acetyl pyrrole, 2-carbethoxy-3-methyl-pyrrole, 2-methyl-5-carbethoxy pyrrole, 2,3-dimethyl-5-carbethoxy pyrrole, 2,4-dimethyl-3-bromo-5-carbethoxy pyrrole, 3-ethyl-4-methyl-5-carbethoxy pyrrole, 3-methyl-4-carbethoxy pyrrole, 2,5-dimethyl-3-carbethoxy pyrrole, 2-methyl-3,5-dicarbethoxy pyrrole, 3-methyl-2,5-dicarbethoxy pyrrole, 2,3-dimethyl-5-carbethoxy pyrrole, 2,3-dimethyl pyrrole, 2,5-dimethyl pyrrole, 2-methyl-5-carboxy pyrrole-4-propionic acid diethyl ester and 2,4-dimethyl pyrrole; with (2) a carbonyl compound selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, paraldehyde, heptaldehyde, laurylaldehyde, stearaldehyde, amino-acetaldehyde, acetone, diethyl-ketone, isobutyl-methyl ketone, 3-pentanone, cyclopentanone, cyclohexanone, pyruvic acid, levulinic acid, glyoxylic acid, benzaldehyde acetophenone, chloroacetone, 2,5-hexane dione and 2-formyl-3-acetyl-4-methyl-5-carbethoxy-pyrrole in the presence of both (a) an acid condensing agent selected from the group consisting of hydriodic acid, aqueous HI, HI in acetic acid, HI in heptane, HBr in acetic acid HCl in acetic acid, H 2 SO 4 in acetic acid, hydrobromic acid, sulfuric acid, and hydrochloric acid; and (b) a reducing agent selected from the group consisting of hydrogen iodide, zinc, zinc in acid, zinc amalgam, stannous bromide, and stannous chloride and when said reducing agent is hydrogen iodide, there may be included also an auxiliary substance selected from the group consisting of red phosphorus, phosphonium iodide, and hypo-phosphorous acid at a temperature sufficient to effect reaction between the substituted pyrrole compound (1) and said carbonyl compound (2) whereby to form from the reactants a derivative of said pyrrole compound in which the carbon of said carbonyl group is attached to the pyrrole ring.
Claim 2
Dependent Claim
258 words
A single step method of ring alkylating a substituted pyrrole compound which comprises the steps of reacting in a liquid system (1) a substituted pyrrole compound selected from the group consisting of 2,4-dimethyl-5-carbethoxy pyrrole, 2,4-dimethyl-3,5-dicarbethoxy pyrrole, 2-methyl-3-carbethoxy pyrrole, 2,4-dimethyl-3-acetyl pyrrole, 2-carbethoxy-3-methyl-pyrrole, 2-methyl-5-carbethoxy pyrrole, 2,3-dimethyl-5-carbethoxy pyrrole, 2,4-dimethyl-3-bromo-5-carbethoxy pyrrole, 3-ethyl-4-methyl-5-carbethoxy pyrrole, 3-methyl-4-carbethoxy pyrrole, 2,5-dimethyl-3-carbethoxy pyrrole, 2-methyl-3,5-dicarbethoxy pyrrole, 3-methyl-2,5-dicarbethoxy pyrrole, 2,3-dimethyl-5-carbethoxy pyrrole, 2,3-dimethyl pyrrole, 2,5-dimethyl pyrrole, 2-methyl-5-carboxy pyrrole-4-propionic acid diethyl ester and 2,4-dimethyl pyrrole; with (2) a carbonyl compound selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, paraldehyde, heptaldehyde, laurylaldehyde, stearaldehyde, amino-acetaldehyde, acetone, diethyl-ketone, isobutyl-methyl ketone, 3-pentanone, cyclopentanone, cyclohexanone, pyruvic acid, levulinic acid, glyoxylic acid, benzaldehyde acetophenone, chloroacetone, 2,5-hexane dione and 2-formyl-3-acetyl-4-methyl-5-carbethoxy-pyrrole in the presence of both (a) an acid condensing agent selected from the group consisting of hydriodic acid, aqueous HI, HI in acetic acid, HI in heptane, HBr in acetic acid HCl in acetic acid, H 2 SO 4 in acetic acid, hydrobromic acid, sulfuric acid, and hydrochloric acid; and (b) a reducing agent selected from the group consisting of hydrogen iodide, zinc, zinc in acid, zinc amalgam, stannous bromide, and stannous chloride and when said reducing agent is hydrogen iodide, there may be included also an auxiliary substance selected from the group consisting of red phosphorus, phosphonium iodide, and hypo-phosphorous acid at a temperature sufficient to effect reaction between the substituted pyrrole compound (1) and said carbonyl compound (2) whereby to form from the reactants a derivative of said pyrrole compound in which the carbon of said carbonyl group is attached to the pyrrole ring.
Claim 3
Dependent Claim
231 words
A single step method of ring alkylating a substituted pyrrole compound which comprises the steps of reacting in a liquid system (1) a substituted pyrrole compound selected from the group consisting of 2,4-dimethyl-5-carbethoxy pyrrole, 2,4-dimethyl-3,5-dicarbethoxy pyrrole, 2-methyl-3 carbethoxy pyrrole, 2,4-dimethyl-3-acetyl pyrrole, 2-carbethoxy-3-methyl-pyrrole, 2-methyl-5-carbethoxy pyrrole, 2, 3-dimethyl-5-carbethoxy pyrrole, 2,4-dimethyl-3-bromo-5-carbethoxy pyrrole, 3-ethyl-4-methyl-5-carbethoxy pyrrole, 3-methyl-4-carbethoxy pyrrole, 2,5-dimethyl-3-carbethoxy pyrrole, 2-methyl-3,5-dicarbethoxy pyrrole, 3-methyl-2,5-dicarbethoxy pyrrole, 2,3-dimethyl-5-carbethoxy pyrrole, 2,3-dimethyl pyrrole, 2,5-dimethyl pyrrole, 2-methyl-5-carboxy pyrrole-4-propionic acid diethyl ester and 2,4-dimethyl pyrrole with (2) a carbonyl compound generated in situ from paraformaldehyde or paraldehyde in the presence of both (a) an acid condensing agent selected from the group consisting of hydriodic acid, aqueous HI, HI in acetic acid, HI in heptane, HBr in acetic acid HCl in acetic acid, H 2 SO 4 in acetic acid, hydrobromic acid, sulfuric acid, and hydrochloric acid; and (b) a reducing agent selected from the group consisting of hydrogen iodide, zinc, zinc in acid, zinc amalgam, stannous bromide, and stannous chloride and when said reducing agent is hydrogen iodide, there may be included also an auxiliary substance selected from the group consisting of red phosphorus, phosphonium iodide, and hypo-phosphorous acid at a temperature sufficient to effect reaction between the substituted pyrrole compound (1) and said carbonyl compound (2) whereby to form from the reactants a derivative of said pyrrole compound in which the carbon of said carbonyl group is attached to the pyrrole ring.
Claim 4
Dependent Claim
231 words
A single step method of ring alkylating a substituted pyrrole compound which comprises the steps of reacting in a liquid system (1) a substituted pyrrole compound selected from the group consisting of 2,4-dimethyl-5-carbethoxy pyrrole, 2,4-dimethyl-3,5-dicarbethoxy pyrrole, 2-methyl-3 carbethoxy pyrrole, 2,4-dimethyl-3-acetyl pyrrole, 2-carbethoxy-3-methyl-pyrrole, 2-methyl-5-carbethoxy pyrrole, 2, 3-dimethyl-5-carbethoxy pyrrole, 2,4-dimethyl-3-bromo-5-carbethoxy pyrrole, 3-ethyl-4-methyl-5-carbethoxy pyrrole, 3-methyl-4-carbethoxy pyrrole, 2,5-dimethyl-3-carbethoxy pyrrole, 2-methyl-3,5-dicarbethoxy pyrrole, 3-methyl-2,5-dicarbethoxy pyrrole, 2,3-dimethyl-5-carbethoxy pyrrole, 2,3-dimethyl pyrrole, 2,5-dimethyl pyrrole, 2-methyl-5-carboxy pyrrole-4-propionic acid diethyl ester and 2,4-dimethyl pyrrole with (2) a carbonyl compound generated in situ from paraformaldehyde or paraldehyde in the presence of both (a) an acid condensing agent selected from the group consisting of hydriodic acid, aqueous HI, HI in acetic acid, HI in heptane, HBr in acetic acid HCl in acetic acid, H 2 SO 4 in acetic acid, hydrobromic acid, sulfuric acid, and hydrochloric acid; and (b) a reducing agent selected from the group consisting of hydrogen iodide, zinc, zinc in acid, zinc amalgam, stannous bromide, and stannous chloride and when said reducing agent is hydrogen iodide, there may be included also an auxiliary substance selected from the group consisting of red phosphorus, phosphonium iodide, and hypo-phosphorous acid at a temperature sufficient to effect reaction between the substituted pyrrole compound (1) and said carbonyl compound (2) whereby to form from the reactants a derivative of said pyrrole compound in which the carbon of said carbonyl group is attached to the pyrrole ring.
Claim 5
Dependent Claim
22 words
A method as claimed in claim 1 in which the pyrrole compound is a pyrrole substituted by at least one methyl group.
Claim 6
Dependent Claim
20 words
A method as claimed in claim 1 in which the pyrrole compound is a pyrrole substituted by two methyl groups.
Claim 7
Dependent Claim
40 words
A method as claimed in claim 1 in which the condensing agent is selected from aqueous HI, HI in acetic acid, HI in heptane, HBr in acetic acid, HCI in acetic acid or H 2 SO 4 in acetic acid.
Claim 8
Dependent Claim
43 words
A method as claimed in claim 1 in which the reducing agent is hydriodic acid, a mixture of hydriodic acid and phosphonium iodide, hydriodic acid and red phosphorous, a mixture of HI and hypophosphorous acid, zinc in acid, stannous bromide or stannous chloride.
Claim 9
Dependent Claim
18 words
A method as claimed in claim 1 in which the condensing agent and reducing agent is hydriodic acid.
References Cited (Backward Citations)
US3271465A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-01-23 | 1981-07-25 | 1982-01-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-01-23 | 1985-07-25 | 1986-01-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-01-23 | 1989-07-25 | 1990-01-24 | $7700.00 | Window Closed / Lapsed |