Patent US1751139A successfully refreshed from Google Patents.
US4567004A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for the preparation of monomethyl-substituted methylene compounds
Assignee: Bayer AG
•
Filing: 1984-07-18
•
Granted: 1986-01-28
•
Expires: 2004-07-18
Abstract
Abstract Monomethyl-substituted methylene compounds are obtained by reacting methylene compounds of the formula ##STR1## in which R 1 and R 2 independently of one another represent --CN, --CO--R 3 , --SO 2 --R 3 or --NO 2 and R 1 can additionally denote -aryl(R 1 ) n , wherein R 3 denotes --OH, alkyl, aralkyl, aryl, alkoxy, aralkoxy or aryloxy, or amino which is substituted by alkyl and/or aralkyl and/or aryl, and furthermore two radicals R 3 together can be an alkylene group, the radical of an aliphatic diol or of an aliphatic diamine or the group --NH--CO--NH-- and n represents 1, 2 or 3, with formaldehyde and with hydrogen in the presence of a condensation catalyst and a hydrogenation catalyst at elevated temperature, the methylene compound being introduced into the liquid phase of the mixture of reactants in the course of the reaction.
Inventors
- 👤 Heinz U. Blank
- 👤 Erich Wolters
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 17:36
CPC Classifications
C; C07; C07C; C07C255/00; C07C253/00; C07C253/30; C07C45/00; C07C45/61; C07C45/67; C07C45/68; C07C45/72; C07C45/75; C07C49/00; C07C49/04; C07C49/12; C07C49/175
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
155 words
A process for the preparation of a monomethyl-substituted methylene compound of the formula ##STR7## which comprises contacting a methylene compound of the formula ##STR8## wherein R 1 and R 2 independently of one another represent --CN, --CO--R 3 , --SO 2 --R 3 and --NO 2 and R 1 can additionally denote --aryl (R 1 ) n' wherein R 3 denotes --OH, alkyl, aralkyl, aryl, alkoxy, aralkoxy or aryloxy, or amino which is unsubstituted or substituted by alkyl and/or aralkyl and/or aryl, and furthermore two radicals R 3 together can be an alkylene group, the radical of an aliphatic diol or of an aliphatic diamine or the group --NH--CO--NH-- and n represents 1, 2 or 3, with formaldehyde and hydrogen in the presence of a condensation catalyst and a hydrogenation catalyst at elevated temperature, wherein the methylene compound is introduced into a liquid phase of the mixture of reactants over the course of the reaction.
Claim 2
Dependent Claim
155 words
A process for the preparation of a monomethyl-substituted methylene compound of the formula ##STR7## which comprises contacting a methylene compound of the formula ##STR8## wherein R 1 and R 2 independently of one another represent --CN, --CO--R 3 , --SO 2 --R 3 and --NO 2 and R 1 can additionally denote --aryl (R 1 ) n' wherein R 3 denotes --OH, alkyl, aralkyl, aryl, alkoxy, aralkoxy or aryloxy, or amino which is unsubstituted or substituted by alkyl and/or aralkyl and/or aryl, and furthermore two radicals R 3 together can be an alkylene group, the radical of an aliphatic diol or of an aliphatic diamine or the group --NH--CO--NH-- and n represents 1, 2 or 3, with formaldehyde and hydrogen in the presence of a condensation catalyst and a hydrogenation catalyst at elevated temperature, wherein the methylene compound is introduced into a liquid phase of the mixture of reactants over the course of the reaction.
Claim 3
Dependent Claim
26 words
A process according to claim 1, wherein the reaction is carried out in the presence of methanol, ethanol, ethyl acetate or methyl ethyl ketone as solvent.
Claim 4
Dependent Claim
17 words
A process according to claim 1, wherein the process is carried out in the presence of methanol.
Claim 5
Dependent Claim
15 words
A process according to claim 1, wherein formaldehyde is employed in the form of paraformaldehyde.
Claim 6
Dependent Claim
46 words
A process according to claim 1, wherein the methylene compound is one of the formula ##STR9## in which R 1 has the meaning given in claim 1 and R 4 represents --CN or --CO--R 3 , wherein R 3 has the meaning given in claim 1.
Claim 7
Dependent Claim
42 words
A process according to claim 1, wherein the methylene compound is one of the formula ##STR10## in which R 4 and R 5 independently of one another represent --CN or --CO--R 3 wherein R 3 has the meaning given in claim 1.
Claim 8
Dependent Claim
40 words
A process according to claim 1, wherein the methylene compound is one of the formula ##STR11## in which R 6 and R 7 independently of one another denote --CN, --CO--C 1 --C 4 -alkyl or CO--O--C 1 -C 4 -alkyl.
Claim 9
Dependent Claim
20 words
A process according to claim 1, wherein the process is carried out at a temperature of 30° to 130° C.
Claim 10
Dependent Claim
23 words
A process according to claim 1, wherein the process is carried out under a partial pressure of hydrogen or 1 to 100 bar.
Claim 11
Dependent Claim
22 words
A process according to claim 8, wherein the process is carried out under a hydrogen partial pressure of 1 to 100 bar.
Claim 12
Dependent Claim
15 words
A process according to claim 1, wherein the hydrogenation catalyst is a noble metal catalyst.
Claim 13
Dependent Claim
18 words
A process according to claim 11, wherein the catalyst comprises platinum, palladium, rhodium, or ruthenium on a support.
Claim 14
Dependent Claim
21 words
A process according to claim 1, wherein the condensation catalyst is a catalyst which catalyzes reactions of the aldol condensation type.
Claim 15
Dependent Claim
28 words
A process according to claim 13, wherein the condensation catalyst is an amine or basic salt or carboxylic acid or hydrogen chloride, sulfuric acid or a Lewis acid.
Claim 16
Dependent Claim
14 words
A process according to claim 1, wherein the methylene compound is methyl cyano acetate.
Claim 17
Dependent Claim
13 words
A process according to claim 1, wherein said methylene compound is diethyl malonate.
Claim 18
Dependent Claim
13 words
A process according to claim 1, wherein said methylene compound is acetyl acetone.
Claim 19
Dependent Claim
13 words
A process according to claim 1, wherein said methylene compound is 4-nitrobenzyl cyanide.
Claim 20
Dependent Claim
12 words
A process according to claim 1, wherein said methylene compound is malodinitrile.
Claim 21
Dependent Claim
70 words
A process according to claim 1, wherein said methylene compound is, malodintrile, a cyano acetate with an alcohol radical, an acetoacetate with an alcohol radical, a nitroacetate with an alcohol radical, a malonate with an alcohol radical, malonic acid, cyanoacetic acid, acetic cyclic ethylene glycol malonate, cyclic malonic acid ethylene-diamide, barbituric acid, acetylacetone, a cyanomethanesulphonate with an alcohol radical, 4-nitrobenzyl cyanide, 2,4-dinitrobenzyl cyanide and a 4-carbethoxyphenylacetate with an alcohol radical.
Claim 22
Dependent Claim
23 words
A process according to claim 1, wherein said methylene compound is added to the liquid phase after a desired reaction temperature is attained.
Claim 23
Dependent Claim
28 words
A process according to claim 1, wherein said methylene compound is added at a rate at which the reaction progresses, or somewhat more slowly than the reaction progresses.
Claim 24
Dependent Claim
26 words
A process according to claim 1, wherein said methylene compound is metered into the liquid phase at a rate corresponding to the rate of hydrogen consumption.
References Cited (Backward Citations)
US3956357A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1989-01-27 | 1989-07-29 | 1990-01-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1993-01-27 | 1993-07-29 | 1994-01-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1997-01-27 | 1997-07-29 | 1998-01-28 | $7700.00 | Window Closed / Lapsed |