Patent US4912232A successfully refreshed from Google Patents.
US4912232A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Preparation of N-hydrocarbylcarbonyl-5-(1-hydrocarbylcarbonyloxy)hydrocarbyl-pyrrolidin-2-one
Assignee: Dow Chemical Co
•
Filing: 1987-08-04
•
Granted: 1990-03-27
•
Expires: 2007-08-04
Abstract
Abstract The invention is a process for the preparation of a N-hydrocarbylcarbonyl-5-(1-hydrocarbylcarbonyloxy)hydrocarbylpyrrolidin-2-one which comprises contacting in an inert nonpolar organic solvent a hydrocarbyloxycarbonylpyrrolidin-2-one with (a) an agent which forms a nitrogen-metal or nitrogen-metalloid bond; (b) a reducing agent; (c) an alkylating agent; and (d) an acylating agent; under conditions such that a N-hydrocarbylcarbonyl-5-(1-hydrocarbylcarbonyloxy)hydrocarbylpyrrolidin-2-one is prepared.
Inventors
- 👤 Michael J. Mullins
- 👤 Edmund P. Woo
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 16:52
CPC Classifications
C; C07; C07D; C07D207/00; C07D207/02; C07D207/18; C07D207/22; C07D207/24; C07D207/26
Claims Analysis
Total Claims: 26
Claim 1
Independent Claim
154 words
A process for the preparation of an N-substituted pyrrolidin-2-one which corresponds to the formula ##STR12## wherein R is separately in each occurrence C 1-20 alkyl, C 7-20 alkaryl, substituted C 1-20 alkyl or substituted C 7-20 alkaryl wherein the substituent is halo, thioalkyl, tert-amino, alkoxy, aryloxy or aralkoxy; R 1 is C 1-20 alkyl or aryl; and R 2 and R 3 are separately in each occurrence hydrogen, a C 1-20 alkyl group or a C 1-20 alkyl group substituted with one or more of the following: halo, thioalkyl, tert-amino, alkoxy, aryloxy or aralkoxy which process comprises contacting in an inert nonpolar organic a pyrrolidin-2-one which corresponds to the formula ##STR13## wherein R 2 and R 3 are as defined above with (a) an agent which forms a nitrogen-metal or nitrogen-metalloid bond; (b) a reducing agent; (c) an alkylating agent; and (d) an acylating agent; under conditions such that the N-substituted pyrrolidin-2-one is prepared.
Claim 2
Dependent Claim
154 words
A process for the preparation of an N-substituted pyrrolidin-2-one which corresponds to the formula ##STR12## wherein R is separately in each occurrence C 1-20 alkyl, C 7-20 alkaryl, substituted C 1-20 alkyl or substituted C 7-20 alkaryl wherein the substituent is halo, thioalkyl, tert-amino, alkoxy, aryloxy or aralkoxy; R 1 is C 1-20 alkyl or aryl; and R 2 and R 3 are separately in each occurrence hydrogen, a C 1-20 alkyl group or a C 1-20 alkyl group substituted with one or more of the following: halo, thioalkyl, tert-amino, alkoxy, aryloxy or aralkoxy which process comprises contacting in an inert nonpolar organic a pyrrolidin-2-one which corresponds to the formula ##STR13## wherein R 2 and R 3 are as defined above with (a) an agent which forms a nitrogen-metal or nitrogen-metalloid bond; (b) a reducing agent; (c) an alkylating agent; and (d) an acylating agent; under conditions such that the N-substituted pyrrolidin-2-one is prepared.
Claim 3
Dependent Claim
151 words
The process of claim 1 wherein the compound which forms a nitrogen-metal or nitrogen-metalloid bond corresponds to the formula M.sub.a M.sup.1.sub.b R.sub.c H.sub.d X.sub.e wherein M and M 1 are separately in each occurence an alkali metal, alkaline earth metal, aluminum, zinc, silicon or boron; each R is independently a C 1-20 alkyl, C 7-20 alkaryl, substituted C 1-20 alkyl or substituted C 7-20 alkaryl wherein the substituent is halo, thioalkyl, tert-amino, alkoxy, aryloxy or aralkoxy group; each X is independently C 1-10 oxyalkyl or halogen; and a, b, c, d and e are separately in each occurrence an integer of from 0 to 4 inclusive; with the proviso that the sum of a and b is 1 or greater and with the further proviso that a, b, c, d and e are such that the sum of the valences of M, M 1 , R, H and X is zero.
Claim 4
Dependent Claim
35 words
The process of claim 2 wherein M and M 1 are separately in each occurrence lithium, sodium, magnesium, aluminum or boron; R is C 1-3 alkyl; and X is chlorine, bromine or C 1-3 alkoxy.
Claim 5
Dependent Claim
27 words
The process of claim 2 wherein M and M 1 are separately in each occurrence lithium or aluminum; R is methyl; and X is chlorine or methoxy.
Claim 6
Dependent Claim
94 words
The process of claim 1 wherein the reducing agent corresponds to the formula M.sub.a M.sup.1.sub.b R.sub.c H.sub.d X.sub.e wherein M and M 1 are separately in each occurrence an alkali metal, alkaline earth metal, aluminum, zinc, silicon or boron; R is alkyl; X is an oxyalkyl or a halogen; a, b, c and e are separately in each occurrence an integer of from 0 to 4 inclusive; and d is an integer of from 1 to 4; with the proviso that the sum of a and b is equal to or greater than 1.
Claim 7
Dependent Claim
19 words
The process of claim 5 wherein R is C 1-10 alkyl; and X is C 1-10 alkoxy or halogen.
Claim 8
Dependent Claim
34 words
The process of claim 5 wherein a and b are 0, 1 or 2; c is 0, 1, 2 or 3; d is 1 to 2; and e is 0, 1, 2 or 3.
Claim 9
Dependent Claim
14 words
The process of claim 5 wherein the reducing agent is a hydride reducing agent.
Claim 10
Dependent Claim
36 words
The process of claim 8 wherein the reducing agent is aluminum hydride, boron hydride, an alkyl aluminum hydride, an alkali or alkaline earth metal hydride, an alkali or alkaline earth metal borohydride, or a hexamethyl bisilazene.
Claim 11
Dependent Claim
24 words
The process of claim 9 wherein the reducing agent is an alkyl aluminum hydride or an alkali or alkaline earth metal alkyl aluminum hydride.
Claim 12
Dependent Claim
73 words
The process of claim 5 wherein the alkylating agent corresponds to the formula M.sub.a R.sub.c X.sub.e wherein each M is independently an alkali metal, an alkaline earth metal, aluminum, zinc, silicon or boron; each R is independently alkyl; each X is a hydrocarbyloxy independently alkoxy or a halogen; a is an integer of 1 to 4; c is an integer of 0 to 4; and e is an integer of 0 to 4.
Claim 13
Dependent Claim
20 words
The process of claim 11 wherein R is C 1-10 alkyl; and X is C 1-10 alkoxy or a halogen.
Claim 14
Dependent Claim
26 words
The process of claim 11 wherein a is 1 or 2; c is 1, 2, 3 or 4; and e is 0, 1, 2 or 3.
Claim 15
Dependent Claim
28 words
The process of claim 5 wherein the alkylating agent is a trialkyl aluminum, an alkyl aluminum halide, an alkyl magnesium halide, a dialkyl magnesium or an alkyl lithium.
Claim 16
Dependent Claim
13 words
The process of claim 5 wherein the alkylating agent is a trialkyl aluminum.
Claim 17
Dependent Claim
42 words
The process of claim 2 wherein the acylating agent is an anhydride which corresponds to the formula ##STR14## or an acyl halide which corresponds to the formula ##STR15## wherein R 1 is a hydrocarbyl radical and X is chloride, bromine or iodine.
Claim 18
Dependent Claim
60 words
The process of claim 1 wherein the 5-alkyloxycarbonylpyrrolidin-2-one is first contacted with (a) an agent which forms a nitrogen-metal or nitrogen-metalloid bond; thereafter the reaction product is contacted with (b) a reducing agent; thereafter the second reaction product is contacted with (c) an alkylating agent; and thereafter the third reaction product is contacted with (d) an acyl chloride or anhydride.
Claim 19
Dependent Claim
53 words
The process of claim 2 wherein the 5-alkyloxycarbonylpyrrolidin-2-one is first contacted with (a) an agent which forms a nitrogen-metal or nitrogen-metalloid bond and (c) an alkylating agent simultaneously; thereafter the reaction product is contacted with (b) a reducing agent; and thereafter the reaction product is contacted with (d) an acyl halide or anhydride.
Claim 20
Dependent Claim
24 words
The process of claim 17 wherein the agent which forms a nitrogen-metal or nitrogen-metalloid bond is the same compound as the alkylating agent (c).
Claim 21
Dependent Claim
24 words
The process of claim 2 wherein the contacting with the alkylating agent occurs at a temperature of between about -78° C. and 35° C.
Claim 22
Dependent Claim
26 words
The process of claim 16 wherein the contacting with the acyl chloride or anhydride occurs at a temperature of between about -30° C. and 25° C.
Claim 23
Dependent Claim
27 words
The process of claim 2 wherein 5-methoxycarbonylpyrrolidin-2-one is contacted in an inert nonpolar organic solvent with trimethyl aluminum and acetic anhydride under conditions sufficient to form N-acetyl-5-(1-acetoxyethyl)-pyrrolidin-2-one.
Claim 24
Dependent Claim
22 words
The process of claim 8 wherein the reducing agent is an alkali metal aluminum hydride or an alkaline earth metal aluminum hydride.
Claim 25
Dependent Claim
26 words
The process of claim 8 wherein the reducing agent is an aluminum alkoxy hydride, an alkali metal alkoxy hydride or an alkaline earth metal alkoxy hydride.
Claim 26
Dependent Claim
21 words
The process of claim 8 wherein the reducing agent is an alkali metal alkyl hydride or an alkaline earth metal hydride.
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) | 1993-03-26 | 1993-09-25 | 1994-03-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-03-26 | 1997-09-25 | 1998-03-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-03-26 | 2001-09-25 | 2002-03-27 | $7700.00 | Window Closed / Lapsed |