US4154952A
Expired / Lapsed
US
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Process for the production of substituted cyclopropane derivatives
Assignee: Individual
•
Filing: 1977-01-31
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Granted: 1979-05-15
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Expires: 1997-01-31
Abstract
Abstract Substituted cyclopropane derivatives are prepared in one step by interreacting an aldehyde, an active methylene compound, a sulfoxonium or sulfonium bromide or iodide, and a strong base in a reaction-inert organic solvent.
Inventors
- 👤 Harry W. Schultz
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 14:58
CPC Classifications
C; C07; C07C; C07C69/00; C07C69/76; C07C69/80; C07C69/82; C07C233/00; C07C233/57; C07C233/58; C07C253/00; C07C253/30; C07C255/00; C07C255/01; C07C255/31; C07C255/45; C07C255/46; C07C69/74; C07C69/743; C07C2601/00; C07C2601/02
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
245 words
The process of making substituted cyclopropane derivatives which comprises: (a) forming a reaction mixture comprising: (1) an aldehyde of the general formula R 1 CHO wherein R 1 is a member of the group consisting of hydrogen, an alkyl group having from 1 to 17 carbon atoms inclusive, phenyl, halophenyl, alkylphenyl having from 1 to 6 carbon atoms inclusive in the alkyl group, alkoxyphenyl having from 1 to 6 carbon atoms inclusive in the alkoxy group, pyridyl, and furfuryl, (2) an active methylene compound of the general formula R 2 CH 2 R 3 wherein R 2 is a member of the group consisting of carbomethoxy, carboethoxy, and nitrile and R 3 is a member of the group consisting of phenyl, carbomethoxy, carboethoxy, nitrile, and amido, or R 2 is carboethoxy and R 3 is acetyl, (3) a sulfur-containing halide of the class consisting of (R 4 CH 2 (CH 3 ) 2 SOX, (R 4 CH 2 )(CH 3 ) 2 SX and (R 4 CH 2 )(CH 2 ) 4 SX where R 4 is hydrogen, carbethoxy, or phenyl and X is a halide ion, (4) a substantially reaction-inert organic solvent for the said aldehyde, active methylene compound and sulfur-containing halide, and (5) a strong base soluble in the said organic solvent, and (b) interacting the constituents of the reaction mixture without distilling the same for substantial water removal thereby converting (them) the reactants to a substituted cyclopropane product of the formula ##STR2##
Claim 2
Dependent Claim
245 words
The process of making substituted cyclopropane derivatives which comprises: (a) forming a reaction mixture comprising: (1) an aldehyde of the general formula R 1 CHO wherein R 1 is a member of the group consisting of hydrogen, an alkyl group having from 1 to 17 carbon atoms inclusive, phenyl, halophenyl, alkylphenyl having from 1 to 6 carbon atoms inclusive in the alkyl group, alkoxyphenyl having from 1 to 6 carbon atoms inclusive in the alkoxy group, pyridyl, and furfuryl, (2) an active methylene compound of the general formula R 2 CH 2 R 3 wherein R 2 is a member of the group consisting of carbomethoxy, carboethoxy, and nitrile and R 3 is a member of the group consisting of phenyl, carbomethoxy, carboethoxy, nitrile, and amido, or R 2 is carboethoxy and R 3 is acetyl, (3) a sulfur-containing halide of the class consisting of (R 4 CH 2 (CH 3 ) 2 SOX, (R 4 CH 2 )(CH 3 ) 2 SX and (R 4 CH 2 )(CH 2 ) 4 SX where R 4 is hydrogen, carbethoxy, or phenyl and X is a halide ion, (4) a substantially reaction-inert organic solvent for the said aldehyde, active methylene compound and sulfur-containing halide, and (5) a strong base soluble in the said organic solvent, and (b) interacting the constituents of the reaction mixture without distilling the same for substantial water removal thereby converting (them) the reactants to a substituted cyclopropane product of the formula ##STR2##
Claim 3
Dependent Claim
10 words
The process of claim 1 wherein the aldehyde comprises benzaldehyde.
Claim 4
Dependent Claim
10 words
The process of claim 1 wherein the aldehyde comprises p-chlorobenzaldehyde.
Claim 5
Dependent Claim
10 words
The process of claim 1 wherein the aldehyde comprises acetaldehyde.
Claim 6
Dependent Claim
11 words
The process of claim 1 wherein the aldehyde comprises dodecyl aldehyde.
Claim 7
Dependent Claim
10 words
The process of claim 1 wherein the aldehyde comprises 2-furaldehyde.
Claim 8
Dependent Claim
12 words
The process of claim 1 wherein the active methylene compound comprises diethylmalonate.
Claim 9
Dependent Claim
12 words
The process of claim 1 wherein the active methylene compound comprises cyanoacetamide.
Claim 10
Dependent Claim
12 words
The process of claim 1 wherein the active methylene compound comprises ethylcyanoacetate.
Claim 11
Dependent Claim
12 words
The process of claim 1 wherein the active methylene compound comprises ethylacetoacetate.
Claim 12
Dependent Claim
37 words
The process of claim 1 including the steps of forming the reaction mixture stepwise by first adding to the organic solvent the strong base, the sulfur-containing halide, and the aldehyde and thereafter adding the active methylene compound.
Claim 13
Dependent Claim
50 words
The process of claim 1 including the steps of first reacting the sulfur-containing halide with the active methylene compound in the organic solvent and in the presence of the strong base and thereafter adding the aldehyde and continuing the reaction for a time sufficient to produce the substituted cyclopropane derivative.
Claim 14
Dependent Claim
53 words
The process of claim 1 including the steps of reacting in the organic solvent the active methylene compound with the strong base, thereby converting it to the corresponding basic salt and thereafter adding the aldehyde and sulfur-containing halide and continuing the reaction for a time sufficient to produce the desired substituted cyclopropane product.
Claim 15
Dependent Claim
52 words
The process of claim 1 wherein there are employed substantially equimolar proportions of the aldehyde, active methylene compound, sulfur-containing halide, and strong base and wherein the reaction is carried out at a temperature of from just above the freezing temperature of the reaction mixture up to and including the boiling temperature thereof.
Claim 16
Dependent Claim
17 words
The process of claim 14 wherein the reaction temperature is from about 20 to about 100° C.
Claim 17
Dependent Claim
11 words
The process of claim 1 wherein the organic solvent is dimethylsulfoxide.
Claim 18
Dependent Claim
56 words
The process of claim 1 wherein the aldehyde is benzaldehyde, the active methylene compound is diethylmalonate, the sulfur-containing halide is trimethylsulfoxonium iodide, and the strong base is sodium hydride, the said reactants being employed in substantially equimolar quantities and the reaction being carried out at a temperature of from about 20° C. to about 100° C.
Claim 19
Dependent Claim
13 words
The process of claim 1 wherein the sulfur-containing halide is carbethoxymethyl dimethylsulfonium bromide.
Claim 20
Dependent Claim
12 words
The process of claim 1 wherein the sulfur-containing halide is methyl-tetramethylene-sulfonium bromide.
Claim 21
Dependent Claim
12 words
The process of claim 1 wherein the sulfur-containing halide is benzyl-tetramethylene-sulfonium bromide.
Claim 22
Dependent Claim
122 words
The process of making substituted cyclopropane derivatives which comprises: (a) forming a reaction mixture comprising substantially equal molecular quantities of benzaldehyde, diethyl malonate, and a sulfur containing halide of the class consisting of (R 4 CH 2 (CH 3 ) 2 SOX, (R 4 CH 2 )(CH 3 ) 2 SX and (R 4 CH 2 )(CH 2 ) 4 SX where R 4 is hydrogen, carbethoxy, or phenyl and X is a halide ion in the presence of a solvent comprising dimethyl sulfoxide and a strong base comprising sodium hydride, and (b) interacting the constituents of the reaction mixture without distilling the same for substantial water removal thereby converting the reactants to a substituted cyclopropane product of the general formula ##STR3##
Claim 23
Dependent Claim
122 words
The process of making substituted cyclopropane derivatives which comprises: (a) forming a reaction mixture comprising substantially equal molecular quantities of benzaldehyde, diethyl malonate, and a sulfur containing halide of the class consisting of (R 4 CH 2 (CH 3 ) 2 SOX, (R 4 CH 2 )(CH 3 ) 2 SX and (R 4 CH 2 )(CH 2 ) 4 SX where R 4 is hydrogen, carbethoxy, or phenyl and X is a halide ion in the presence of a solvent comprising dimethyl sulfoxide and a strong base comprising sodium hydride, and (b) interacting the constituents of the reaction mixture without distilling the same for substantial water removal thereby converting the reactants to a substituted cyclopropane product of the general formula ##STR3##
Claim 24
Dependent Claim
13 words
The process of claim 21 wherein the sulphur containing halide comprises trimethyl-sulfoxonium iodide.
References Cited (Backward Citations)
US3397223A
Cited
US4083863A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-05-14 | 1982-11-13 | 1983-05-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-05-14 | 1986-11-13 | 1987-05-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-05-14 | 1990-11-13 | 1991-05-15 | $7700.00 | Window Closed / Lapsed |