CA1171098A - Process for producing cyclopropyl carboxylic amides - Google Patents
Process for producing cyclopropyl carboxylic amidesInfo
- Publication number
- CA1171098A CA1171098A CA000381429A CA381429A CA1171098A CA 1171098 A CA1171098 A CA 1171098A CA 000381429 A CA000381429 A CA 000381429A CA 381429 A CA381429 A CA 381429A CA 1171098 A CA1171098 A CA 1171098A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- present
- reaction
- approximately
- ammonia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
Abstract
ABSTRACT OF THE DISCLOSURE
Cyclopropyl carboxylic amides are interesting inter-mediate products particularly for the production of the corres-ponding amines, which are in turn a basis for herbicides.
According to the present invention the cyclopropyl carboxylic amides are produced by reacting .gamma.-chloro butyric esters with alcoholates in the presence of liquid ammonia. The products are obtained in high yields.
Cyclopropyl carboxylic amides are interesting inter-mediate products particularly for the production of the corres-ponding amines, which are in turn a basis for herbicides.
According to the present invention the cyclopropyl carboxylic amides are produced by reacting .gamma.-chloro butyric esters with alcoholates in the presence of liquid ammonia. The products are obtained in high yields.
Description
71~9~
The present invention relates to a process for pro-ducing cyclopropyl carboxylic amides ~rom the corresponding ~-chloro butyric acid estersO
Cyclopropyl carboxylic amides can be easily converted with the aid of dehydrating agen~s into the corresponding nitriles, which serve in turn as a basis for the production of various amines containing cyclopropyl groupsO sy hydrogenating the nitriles they can be converted into the corresponding methyl amines. When operating in the presence of other primary amines, then secondary amines are obtained. I'hese secondary amines are, for example, components of important herbicides. Thus, for examp]e, cyclopropyl-methyl-N-propyl amine is used for the synthesis of a herbicide for soybeans (as disclosed in U.S.
Patent No. 3,546,295).
Cyclopropane carboxylic amides can be obtained, for example, by reacting the cyclopropane carboxylic esters with ammonia uDder pressure at elevated temperatures, for example, 80C (as disclosed in German Auslegeschrift No. 1,939,759).
The fact thatthisprocess isbased on cyclopropane ~erivatives 20 ' is a disadvantage.
The production of cyclopropane carboxylic esters by cyclization of ~-chloro-butyric esters is also ~nown., For exam-ple, the latter ester is heated with t-sodium amylate in t-amyl alcohol for four hours to the boiling point. The cyclo-propane carboxylic ethyl ester is thus obtained in a yield of only 45% (Julia et al, ~ull. Soc. Chemïc (France) 1960, page 306 ff.). When reacting ~-chloro-capronic ester with sodium amide in ether, then the 2-methyl-cyclopropane carboxylic ester is obtained in a yield of 85% after a reaction time of 4 3U to 5 days (Am. Soc. 81, page 1660-66).
' Finally, the reaction o~ ~-chloro-butyric ethyl ester with sodium methylate is also known. H~wever~ yields of only 1~L71~9~
66% are obtained (Bunce et al, Organic Preparations and Procedures 6, page 193-96 (1974)). The production of cyclopropane carboxy lic ethyl ester from 4-bromo-butyric ester by cyclization with NaH was also described. A yield of 88~ is obtained (I. Chem. Eng.
Data 14, 396 (1969)).
Finally it is also known to produce cyclopropyl carboxylic amide solutions by a process in which in a first stage the reaction of 4-chloro-butyric methyl ester with sodium methylate is carried out in an inert gas atmosphere in a non-reactive organic liquid, for example, toluene, under anhydrousconditions. In this case the yields are 92~ of the theoretical yield (German Auslegeschrift 19 39 759).
The process of these prior publications are very cumbersome and costly to carry out.
It has now been found that cyclopropyl carboxylic amides having the general formula (I) ~ -CH~
Rl~ CH -- - ~C ~ - CON 2 (I) can be produced continuously, when required, if a ~-ch~oro butyric ester having the general formula (II) R-l Rl ~ CHCl - CH2 ~ C~ ~ CR2 (II) is reacted under anhydrous conditions with sodium or potassium methylate or ethylate in methanol or ethanol in the presence o~ uid ammonia and by maintaining a temperature above the boiling temperature of the alcohol used, when required by applying pressure.
In the general formulae (I) and (II) Rl represents a hydrogen atom or the methyl group and R2 represents the methyl or ethyl group.
It is very surprising that while maintaining t~e above reaction conditions the desired cyclopropane carboxylic amides ~7~ 9~
are obtained~in the highest yields from ~-halogen butyric esters with the Na/K alcoholates of methanol or ethanol alone in the methanol or ethanol.
The process according to the presen-t invention thus has the following advantages:
1. It is a single-stage process for producing cyclo-propane carboxylic amides, while heretofore only two-stage processes were available for this purpose.
The present invention relates to a process for pro-ducing cyclopropyl carboxylic amides ~rom the corresponding ~-chloro butyric acid estersO
Cyclopropyl carboxylic amides can be easily converted with the aid of dehydrating agen~s into the corresponding nitriles, which serve in turn as a basis for the production of various amines containing cyclopropyl groupsO sy hydrogenating the nitriles they can be converted into the corresponding methyl amines. When operating in the presence of other primary amines, then secondary amines are obtained. I'hese secondary amines are, for example, components of important herbicides. Thus, for examp]e, cyclopropyl-methyl-N-propyl amine is used for the synthesis of a herbicide for soybeans (as disclosed in U.S.
Patent No. 3,546,295).
Cyclopropane carboxylic amides can be obtained, for example, by reacting the cyclopropane carboxylic esters with ammonia uDder pressure at elevated temperatures, for example, 80C (as disclosed in German Auslegeschrift No. 1,939,759).
The fact thatthisprocess isbased on cyclopropane ~erivatives 20 ' is a disadvantage.
The production of cyclopropane carboxylic esters by cyclization of ~-chloro-butyric esters is also ~nown., For exam-ple, the latter ester is heated with t-sodium amylate in t-amyl alcohol for four hours to the boiling point. The cyclo-propane carboxylic ethyl ester is thus obtained in a yield of only 45% (Julia et al, ~ull. Soc. Chemïc (France) 1960, page 306 ff.). When reacting ~-chloro-capronic ester with sodium amide in ether, then the 2-methyl-cyclopropane carboxylic ester is obtained in a yield of 85% after a reaction time of 4 3U to 5 days (Am. Soc. 81, page 1660-66).
' Finally, the reaction o~ ~-chloro-butyric ethyl ester with sodium methylate is also known. H~wever~ yields of only 1~L71~9~
66% are obtained (Bunce et al, Organic Preparations and Procedures 6, page 193-96 (1974)). The production of cyclopropane carboxy lic ethyl ester from 4-bromo-butyric ester by cyclization with NaH was also described. A yield of 88~ is obtained (I. Chem. Eng.
Data 14, 396 (1969)).
Finally it is also known to produce cyclopropyl carboxylic amide solutions by a process in which in a first stage the reaction of 4-chloro-butyric methyl ester with sodium methylate is carried out in an inert gas atmosphere in a non-reactive organic liquid, for example, toluene, under anhydrousconditions. In this case the yields are 92~ of the theoretical yield (German Auslegeschrift 19 39 759).
The process of these prior publications are very cumbersome and costly to carry out.
It has now been found that cyclopropyl carboxylic amides having the general formula (I) ~ -CH~
Rl~ CH -- - ~C ~ - CON 2 (I) can be produced continuously, when required, if a ~-ch~oro butyric ester having the general formula (II) R-l Rl ~ CHCl - CH2 ~ C~ ~ CR2 (II) is reacted under anhydrous conditions with sodium or potassium methylate or ethylate in methanol or ethanol in the presence o~ uid ammonia and by maintaining a temperature above the boiling temperature of the alcohol used, when required by applying pressure.
In the general formulae (I) and (II) Rl represents a hydrogen atom or the methyl group and R2 represents the methyl or ethyl group.
It is very surprising that while maintaining t~e above reaction conditions the desired cyclopropane carboxylic amides ~7~ 9~
are obtained~in the highest yields from ~-halogen butyric esters with the Na/K alcoholates of methanol or ethanol alone in the methanol or ethanol.
The process according to the presen-t invention thus has the following advantages:
1. It is a single-stage process for producing cyclo-propane carboxylic amides, while heretofore only two-stage processes were available for this purpose.
2~ The use of only one solvent.
3. Large savings in time and energy because of the much more rapid reaction.
4. E~igher yields than in the two-stage process.
5. The use of the very costly and sensitive sodium methyl powder, whose handling is hazardous and whose dusts are hi~hl~ toxic, is dispensed with. Instead, the much less hazardous sodium methylate solutions are utilized.
The alcoholates are suitably used in at least equi-molar amounts. However, it is favourable to use an e~cess of approximately 10~.
The anhydrous ammonia is also used in at least equi--mo~ar amounts, but the use of an excess of 100 to 200% is advantageous.
The reaction according to the present invention can be carried out at a temperature between approximately 90C
and approximately 200C, but the temperature range between 140 and 160C is preferred.
~hen carrying out the process discontinuously the procedure may be such that, for example, per mole o~ y-chloro carboxylic ester 1 to 1.1 moles of alcoholate dissolved in al-cohol are put into a pressurevessel (auto clave). Ammonia gas is then forced into the closed autoclave. It is advanta~eous to malntain the excess pressure mentioned abo~e~ The autoclave 7~ ~9~
is then heated upO As soon as the temperature range be-tween 90C and approximately 200C is reached the halogen ester is pumped into the autoclave. The reaction is completed within a few minutes. On completion of ~he~reaction heating is continued for a short time, whereupon the product is further treated in a manner known per se.
In the continuous method the reaction described above is carried out in a simple manner in a pressure tube coil.
The progress of this reaction is surprising since it is known that the reaction of y-chloro butyl esters with sodium alcoholate produces only small yields and since it is also known that the y-chloro butyric esters react with ammonia to pyrroli-dones.
The r-chloro carboxylic esters required as the starting material for the process according to the present invention can be produced from the corresponding lactones or ~-hydroxy or chloro carboxylic acids or chlorG carboxylic chlorldes by means of processes known per se (Liebigs Ann. 596, page 163-164;
Synthesis 1973, page 538-539; Federal German Patent 80~,567;
French Patent 1,080,261; U.S. Patent 3,927,074).
~- The present invention will be further illustrated by way of the following Examples.
Example l 594 g of sodium methylate in 1500 ml of methanol are put into a 5-litre stirring autoclave, which is then closed and 350 g of ammonia are injected from a steel cylinder, followed by heating to 145C. Within two hours 1365 kg of ~-chlorobutyric methyl ester are pumped in, followed by heating for one hour and cooling. The autoclave is emptied and the mixture is neutraliz-ed with concentrated sulphuric acid, whereupon the ammonium chloride and ammonium sulphate are filtered with suction and washed wi~h water. The filtrate is then further processed.
o ~ ~
799 g of cyclopropane amide are obtained/ corresponding to 94% of the theoretical yield; white crystals, m.p.= 120 to 121C.
Example 2 50 y of sodium are dissolved in 1 litre of absolute ethanol. While the solution is still warm it is put into a 2-litre autoelave, which is then closed, whereupon 80 g of ammonia are injected. The autoclave is heated up to 145-150C. 301 g of y-chloroeapronic methyl ester are then pumped in within one hour, followed by heating for one hour. The mixture i5 then further treated as described in Example 1.
180.4 g of 2~methyl cyclopropane carboxylic amide is obtained; m.p.= 120C, white crystals.
Yield: 91.1~ of the theoretical yield Analysis: C5HgON (M=a3) eomputed: C60.6 H9.1 N14.1 obtained: 60.8 9.0 13.9 Exa ~
55.2 g of sodium are dissolvea in 1 litre of methanol and the solution is put into a 2-litre autoelave, whieh is then elosed, whereupon 100 g o ammonia are injected. This is followed by heating to 140C and at this temperature 301 g of a-methyl-y-chloro butyric methyl ester are pumped in within 40 minutes, followed by heating for one hour and further proeessing a$ in Example 1.
174~5 g of l-methyl eyelopropane earboxylie amide are obtained; m.p. - 133C, wh~te erystals.
Yield: 88.1% of the theoretieal yield.
Analysis: C5HgON ~M=99) computed: C60.6 H9.1 N14.1 obtained: 60.7 8.9 14.0 Comparison Example a) 178.2 g of sodium methylate in 570 ml of methanol are put into a 2-litre stirring vessel having an agitator. Within one hour 409.5 g of y-chloro butyrlc methyl ester are added drop-wise wlth reflux followed by heating for two hours with reflux.
Thi,s is followed by cooling, whereupon 750 ml of methylene chloride are added. 1.5 litres of water are then added drop-wise. The vessel is then shaken out and the CH2CQ2 layer is separated. After further treatment 198.6 g of cyclopropane carboxylic methyl ester are obtained; b.p. = 114 to 115C.
Yield: 66.2%
The treatment of the residue by distlllation yields 81 g of y-methoxy butyric methyl ester (20.4% of the theoretical yield) and 36 g (i.e., 8.8%) of non-reacted y-chloro butyric ' mëthyl ester'as well as 6.1 g of~butyrolactone.
h) 500 ml of methanol are put into a 2-litre autoclave, which is then closed, whereupon 200 ml of NH3 are injected from the pressuxe ~ottle. This is followed by heating to 150C, whereupon 273 g of y-chlorobutyric methyl ester are pumped in ~ , within one hour, followed by heating for one hour and cooling.
The autoclave is then opened and the ammonium chloride formed (94 g) is filtered with suction. The filtrate is then concen-trated by evaporation. 175.5 g of a clear water-soluble oil remain. At b.p.lo 128 to 129C vacuum distillation yields 127.1 g of pyrrolidone-2, i.e., 74.7% of the theoretical yield.
' 30
The alcoholates are suitably used in at least equi-molar amounts. However, it is favourable to use an e~cess of approximately 10~.
The anhydrous ammonia is also used in at least equi--mo~ar amounts, but the use of an excess of 100 to 200% is advantageous.
The reaction according to the present invention can be carried out at a temperature between approximately 90C
and approximately 200C, but the temperature range between 140 and 160C is preferred.
~hen carrying out the process discontinuously the procedure may be such that, for example, per mole o~ y-chloro carboxylic ester 1 to 1.1 moles of alcoholate dissolved in al-cohol are put into a pressurevessel (auto clave). Ammonia gas is then forced into the closed autoclave. It is advanta~eous to malntain the excess pressure mentioned abo~e~ The autoclave 7~ ~9~
is then heated upO As soon as the temperature range be-tween 90C and approximately 200C is reached the halogen ester is pumped into the autoclave. The reaction is completed within a few minutes. On completion of ~he~reaction heating is continued for a short time, whereupon the product is further treated in a manner known per se.
In the continuous method the reaction described above is carried out in a simple manner in a pressure tube coil.
The progress of this reaction is surprising since it is known that the reaction of y-chloro butyl esters with sodium alcoholate produces only small yields and since it is also known that the y-chloro butyric esters react with ammonia to pyrroli-dones.
The r-chloro carboxylic esters required as the starting material for the process according to the present invention can be produced from the corresponding lactones or ~-hydroxy or chloro carboxylic acids or chlorG carboxylic chlorldes by means of processes known per se (Liebigs Ann. 596, page 163-164;
Synthesis 1973, page 538-539; Federal German Patent 80~,567;
French Patent 1,080,261; U.S. Patent 3,927,074).
~- The present invention will be further illustrated by way of the following Examples.
Example l 594 g of sodium methylate in 1500 ml of methanol are put into a 5-litre stirring autoclave, which is then closed and 350 g of ammonia are injected from a steel cylinder, followed by heating to 145C. Within two hours 1365 kg of ~-chlorobutyric methyl ester are pumped in, followed by heating for one hour and cooling. The autoclave is emptied and the mixture is neutraliz-ed with concentrated sulphuric acid, whereupon the ammonium chloride and ammonium sulphate are filtered with suction and washed wi~h water. The filtrate is then further processed.
o ~ ~
799 g of cyclopropane amide are obtained/ corresponding to 94% of the theoretical yield; white crystals, m.p.= 120 to 121C.
Example 2 50 y of sodium are dissolved in 1 litre of absolute ethanol. While the solution is still warm it is put into a 2-litre autoelave, which is then closed, whereupon 80 g of ammonia are injected. The autoclave is heated up to 145-150C. 301 g of y-chloroeapronic methyl ester are then pumped in within one hour, followed by heating for one hour. The mixture i5 then further treated as described in Example 1.
180.4 g of 2~methyl cyclopropane carboxylic amide is obtained; m.p.= 120C, white crystals.
Yield: 91.1~ of the theoretical yield Analysis: C5HgON (M=a3) eomputed: C60.6 H9.1 N14.1 obtained: 60.8 9.0 13.9 Exa ~
55.2 g of sodium are dissolvea in 1 litre of methanol and the solution is put into a 2-litre autoelave, whieh is then elosed, whereupon 100 g o ammonia are injected. This is followed by heating to 140C and at this temperature 301 g of a-methyl-y-chloro butyric methyl ester are pumped in within 40 minutes, followed by heating for one hour and further proeessing a$ in Example 1.
174~5 g of l-methyl eyelopropane earboxylie amide are obtained; m.p. - 133C, wh~te erystals.
Yield: 88.1% of the theoretieal yield.
Analysis: C5HgON ~M=99) computed: C60.6 H9.1 N14.1 obtained: 60.7 8.9 14.0 Comparison Example a) 178.2 g of sodium methylate in 570 ml of methanol are put into a 2-litre stirring vessel having an agitator. Within one hour 409.5 g of y-chloro butyrlc methyl ester are added drop-wise wlth reflux followed by heating for two hours with reflux.
Thi,s is followed by cooling, whereupon 750 ml of methylene chloride are added. 1.5 litres of water are then added drop-wise. The vessel is then shaken out and the CH2CQ2 layer is separated. After further treatment 198.6 g of cyclopropane carboxylic methyl ester are obtained; b.p. = 114 to 115C.
Yield: 66.2%
The treatment of the residue by distlllation yields 81 g of y-methoxy butyric methyl ester (20.4% of the theoretical yield) and 36 g (i.e., 8.8%) of non-reacted y-chloro butyric ' mëthyl ester'as well as 6.1 g of~butyrolactone.
h) 500 ml of methanol are put into a 2-litre autoclave, which is then closed, whereupon 200 ml of NH3 are injected from the pressuxe ~ottle. This is followed by heating to 150C, whereupon 273 g of y-chlorobutyric methyl ester are pumped in ~ , within one hour, followed by heating for one hour and cooling.
The autoclave is then opened and the ammonium chloride formed (94 g) is filtered with suction. The filtrate is then concen-trated by evaporation. 175.5 g of a clear water-soluble oil remain. At b.p.lo 128 to 129C vacuum distillation yields 127.1 g of pyrrolidone-2, i.e., 74.7% of the theoretical yield.
' 30
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing a cyclopropyl carboxylic amide having the general formula (I) (I) wherein R1 represents a hydrogen atom or a CH3 group,which comprises a .gamma.-chloro butyric ester having the general formula (II) (II) wherein R1 has the meanings defined above and R2 represents the methyl or ethyl group under anhydrous conditions with an alcoholate selected from sodium and potassium methylate or ethylate in methanol or ethanol in the presence of ammonia at a temperature above the boiling point of the alcohol while applying pressure.
2. A process according to claim 1, in which the alcoholate is present in at least equimolar amounts.
3. A process according to claim 2, in which the alcoholate is present in an excess of 10%.
4. A process according to claim 1, 2 or 3, in which the anhydrous ammonia is present in an at least equimolar amount.
5. A process according to claim 1, 2 or 3, in which the anhydrous ammonia is present in an excess of 100 to 200%.
6. A process according to claim 1, 2 or 3, in which the reaction is carried out at a temperature between approximately 90°C and approximately 200°C.
7. A process according to claim 1, 2 or 3, in which the reaction is carried out at a temperature between approximately 140°C and 160°C.
8. A process according to claim 1, 2 or 3, which is effected on a continuous basis.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3026094.7-42 | 1980-07-10 | ||
| DE19803026094 DE3026094C2 (en) | 1980-07-10 | 1980-07-10 | Process for the preparation of cyclopropanecarboxamides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1171098A true CA1171098A (en) | 1984-07-17 |
Family
ID=6106838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000381429A Expired CA1171098A (en) | 1980-07-10 | 1981-07-09 | Process for producing cyclopropyl carboxylic amides |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0043949B1 (en) |
| JP (1) | JPS5748952A (en) |
| CA (1) | CA1171098A (en) |
| DE (1) | DE3026094C2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068428A (en) * | 1988-10-28 | 1991-11-26 | Bayer Aktiengesellschaft | Process for the preparation of cyclopropanecarboxamide |
| US5739399A (en) * | 1995-12-20 | 1998-04-14 | Bayer Aktiengesellschaft | Process for the preparation of cyclopropanecarboxylic acid amides |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590292A (en) * | 1985-06-10 | 1986-05-20 | Ciba-Geigy Corporation | Process for the manufacture of cyclopropylamine |
| DE4400328A1 (en) * | 1994-01-07 | 1995-07-13 | Huels Chemische Werke Ag | Process for the preparation of cyclopropanecarboxamide |
| DE19830633A1 (en) * | 1998-07-09 | 2000-01-13 | Degussa | Process for the preparation of cyclopropylamine |
| US6552217B2 (en) * | 2000-08-01 | 2003-04-22 | Eastman Chemical Company | Process for the preparation of alkyl 1-methylcyclopropanecarboxylate |
| CN116508749A (en) * | 2023-07-03 | 2023-08-01 | 四川科宏达集团有限责任公司 | Herbicide synergistic auxiliary agent and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES370147A1 (en) * | 1968-08-29 | 1971-04-01 | Gulf Research Development Co | A procedure to manufacture ciclopropilamin. (Machine-translation by Google Translate, not legally binding) |
| US3711549A (en) * | 1970-05-19 | 1973-01-16 | Gulf Research Development Co | Process for manufacturing cyclopropylamine |
-
1980
- 1980-07-10 DE DE19803026094 patent/DE3026094C2/en not_active Expired
-
1981
- 1981-06-24 EP EP19810104876 patent/EP0043949B1/en not_active Expired
- 1981-07-08 JP JP10575581A patent/JPS5748952A/en active Pending
- 1981-07-09 CA CA000381429A patent/CA1171098A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068428A (en) * | 1988-10-28 | 1991-11-26 | Bayer Aktiengesellschaft | Process for the preparation of cyclopropanecarboxamide |
| US5739399A (en) * | 1995-12-20 | 1998-04-14 | Bayer Aktiengesellschaft | Process for the preparation of cyclopropanecarboxylic acid amides |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3026094A1 (en) | 1982-01-28 |
| JPS5748952A (en) | 1982-03-20 |
| EP0043949B1 (en) | 1983-10-05 |
| DE3026094C2 (en) | 1983-01-05 |
| EP0043949A1 (en) | 1982-01-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |