Claims
- 1. Process for the preparation of compounds of Formula I ##STR4## wherein R is C.sub.1-5 haloalkyl;
- Y is oxygen or sulfur;
- R.sub.2 is C.sub.1-10 alkyl, alkenyl, alkynyl, alkoxyalkyl, C.sub.3-7 cycloalkyl, lower alkylcycloalkyl or cycloalkenyl, C.sub.6-12 aryl or aralkyl, or said R.sub.1 members substituted with C.sub.1-4 lower alkylthio, halogen, hydroxy, nitro or cyano;
- R.sub.2, R.sub.3 and R.sub.4 are independently hydrogen, halogen, C.sub.1-6 alkyl, haloalkyl, alkoxy or alkoxyalkyl,
- n is an integer from 0-3 inclusive, which comprises performing at least one sequence of reaction/separation operations comprising:
- (A) reacting a compound of Formula II ##STR5## with a compound of Formula III
- R.sub.1 YH (III)
- wherein R, R.sub.1 -R.sub.4, Y, and n are as defined above and X is halogen, in the absence of an acid-binding agent for period of time required to reach equilibrium and thereafter without delay,
- (B) directing an effluent stream of the reaction mixture from Step (A) to a separation zone wherein means are employed to rapidly remove a gaseous mixture containing a complex of by-product HX with said compound of Formula III from a liquid product stream comprising predominantly said compound of Formula I.
- 2. Process according to claim 1 in which said reaction/separation process is carried out in a sequence of two stages which comprises:
- Performing the (A) and (B) reaction/separation operations as described in claim 1;
- (C) directing said product stream from said first separation zone to a second reaction zone into which is also introduced an additional quantity of said compound of Formula III to react with said unreacted compound of Formula II in the absence of an acid-binding agent for a period of time required to reach equilibrium and thereafter without delay;
- (D) directing an effluent stream of the reaction mixture of Step (C) to a second separation zone wherein means are employed to rapidly remove a gaseous mixture containing substantially all of the remaining by-product HX as a complex with said compound of Formula III and a liquid product stream comprised of said compound of Formula I and tract impurities.
- 3. Process according to claim 1 wherein said reaction/separation process sequence is repeated a plurality of times to assure complete conversion of said compound of Formula II to said compound of Formula I.
- 4. Process according to claim 2 wherein Step (A) is conducted at a temperature within the range of from about -25.degree. to 125.degree. C.
- 5. Process according to claim 2 wherein Step (C) is conducted at temperatures within the range of from about -25.degree. to 175.degree. C.
- 6. Process according to claim 2 wherein the compound of Formula III is used in an amount corresponding to a molar ratio of >1:1 relative to the compound of Formula II.
- 7. Process according to claim 6 wherein said molar ratio is within the range of about 2-100:1.
- 8. Process according to claim 2 wherein said complex of HX with compound of Formula III from Step (D) is fed to a recovery system from which said compound of Formula III is removed from said hydrogen halide, purified and recycled to Steps (A) and/or (C).
- 9. Process according to claim 1 wherein temperatures in Steps (B) and (D) are within the range of about 50.degree. C. to 175.degree. C. and pressures are within the range of about 1.0 to 300 mm Hg absolute.
- 10. Process according to claim 1, wherein in said formulae
- X is chlorine;
- Y is oxygen;
- R is monohalomethyl,
- R.sub.1 is C.sub.1-6 alkyl;
- R.sub.2, R.sub.3 and R.sub.4 are independently hydrogen, halogen, C.sub.1-6 alkyl, haloalkyl, alkoxy or alkoxyalkyl, and
- n is an integer of 0-2, inclusive.
- 11. Process according to claim 10 wherein in Formula I
- R.sub.1, R.sub.2 and R.sub.3 are C.sub.1-6 alkyl;
- R is monochloromethyl; and
- n is zero.
- 12. Process according to claim 11 wherein
- R.sub.1 is methyl, ethyl, propyl or butyl, and
- R.sub.2 and R.sub.3 are methyl or ethyl.
- 13. Process according to any of claims 1, 2, 3, 4, 5, 6, 11 or 12 wherein said compound of Formula III is ethanol.
- 14. Process for preparation and recovery of alachlor or butachlor which comprises performing at least one sequence of reaction/separation operations comprising:
- (A) reacting methanol or butanol with 2',6'-diethyl-N-(chloromethyl)-2-chloroacetanilide at a molar ratio of about 2-100:1 at temperatures within the range of from about 25.degree.-65.degree. for a period of time required to reach equilibrium within about 15-30 minutes in the absence of added acid binders, and thereafter without delay;
- (B) directing an effluent stream of the reaction mixture from Step (A) to a separation zone wherein means are employed to rapidly remove a gaseous mixture containing a complex of HCl and methanol or butanol and a liquid product stream comprising predominantly alachlor or butachlor.
- 15. Process according to claim 14 wherein said reaction/separation sequence is repeated a plurality of times to assure substantially complete conversion of 2',6'-diethyl-N-(chloromethyl)-2-chloroacetanilide to alachlor or butachlor.
- 16. Process according to claim 15 which comprises:
- (A) reacting in a first reaction zone maintained at about 25.degree.-65.degree. C. methanol or butanol with 2',6'-diethyl-N-(chloromethyl)-2-chloroacetanilide at a molar feed ratio of about 2-10:1 in the absence of added acid binders for a period of time required to reach equilibrium within about 15 to 30 minutes, and therafter without delay;
- (B) directing an effluent stream of the reaction mixture of Step (A) to a flash distillation zone maintained at temperatures and pressures within the ranges of about 50.degree.-100.degree. C. and 30-300 mm Hg absolute from which is removed a gaseous mixture containing a complex of methanol or butanol and most of by-product HCl and a liquid product stream comprising predominantly alachlor or butachlor and unreacted 2',6'-diethyl-N-(chloromethyl)-2-chloroacetanilide.
- (C) directing said product stream from said first separation zone to a second reaction zone maintained at about 25.degree.-65.degree. C. into which is also introduced an additional quantity of methanol or butanol to react with said unreacted 2',6'-diethyl-N-(chloromethyl)-2-chloroacetanilide in an amount corresponding to the amount used in first reaction zone in the absence of acid binders for a period of time required to reach equilibrium within about 15 to 30 minutes and thereafter without delay;
- (D) directing an effluent stream of the reaction mixture of Step (C) to a second flash distillation zone maintained at temperatures and pressures within the ranges of about 50.degree.-100.degree. C. and 30-300 mm Hg absolute from which is removed a gaseous mixture containing a complex comprising methanol or butanol and substantially all of the remaining by-product HCl and a liquid product stream comprised of alachlor or butachlor and trace impurities.
- 17. Process according to claim 16 wherein said complex of methanol or butanol and HCl from Steps (B) and (D) are combined and fed to a methanol or butanol recovery system from which HCl is removed and recovered methanol or butanol is purified and recycled to Steps (A) and/or (C).
- 18. Process according to claim 17 wherein the residence time of said reaction mixture in said flash distillation zones of Steps (B) and (D) is <0.5 minute.
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Continuation of Ser. No. 07/218,777, filed Jul. 14, 1988, which is a Continuation-in-part of Ser. No. 07/013,597 filed Feb. 11, 1987, which is a Continuation of Ser. No. 06/799,383 filed Nov. 18, 1985, which is a Continuation of Ser. No. 06/591,644 filed Mar. 20, 1984, which is a Continuation Ser. No. 06/460,508 filed Jan. 24, 1983 which is a Continuation of Ser. No. 05/844,542 filed Oct. 26, 1977, which is a Continuation-in-part of Ser. No. 05/755,279 filed Dec. 29, 1976, all abandoned.
US Referenced Citations (13)
Foreign Referenced Citations (3)
Number |
Date |
Country |
816559 |
Dec 1974 |
BEX |
18706 |
Mar 1978 |
ILX |
103351 |
Jun 1983 |
JPX |
Continuations (5)
|
Number |
Date |
Country |
Parent |
218777 |
Jul 1988 |
|
Parent |
799383 |
Nov 1985 |
|
Parent |
591644 |
Mar 1984 |
|
Parent |
460508 |
Jan 1983 |
|
Parent |
844542 |
Oct 1977 |
|
Continuation in Parts (2)
|
Number |
Date |
Country |
Parent |
13597 |
Feb 1987 |
|
Parent |
755279 |
Dec 1976 |
|