AU2002314078A1 - Process for the preparation of alkyl-N-(3-dimethylamino)alkylcarbamates - Google Patents
Process for the preparation of alkyl-N-(3-dimethylamino)alkylcarbamatesInfo
- Publication number
- AU2002314078A1 AU2002314078A1 AU2002314078A AU2002314078A AU2002314078A1 AU 2002314078 A1 AU2002314078 A1 AU 2002314078A1 AU 2002314078 A AU2002314078 A AU 2002314078A AU 2002314078 A AU2002314078 A AU 2002314078A AU 2002314078 A1 AU2002314078 A1 AU 2002314078A1
- Authority
- AU
- Australia
- Prior art keywords
- dimethylamino
- propyl
- alkyl
- chloroformate
- process according
- 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.)
- Granted
Links
Description
PROCESS FOR THE PREPARATION OF ALKYL-N-(3-DI ETHYLAMINO)ALKYLCARBAMATES
Description
This invention relates to a process for the preparation of alkyl-N-(3- dimethylamino)alkylcarbamates.
Alkyl-N-(3-dimethylamino)alkylcarbamates and their salts can be used as fungicides (see
GB 1 212 708, ZA 68 5172, DE 1 567 169, DE 1643 040). N-propyl-3-(dimethylamino)n-propylcarbamate is a well known fungicidal active ingredient and is normally sold as the hydrochloride salt. This compound is normally prepared by reacting 3-(dimethylamino)n-propylamine with n-propyl chloroformate in inert solvents including toluene and ethers.
We have now found a new process which is characterised by carrying out the reaction at varying temperatures in alcohols or mixtures of alcohols with water, inert organic solvents or mixtures thereof.
Thus the invention provides a process for the preparation of alkyl-N-(3- dimethylamino)alkylcarbamates which comprises reacting an alkyl-chloroformate in an aliphatic (Oι-Cs)-alcohol. Preferably, the process of the present invention is used for the preparation of N-propyl-3-
(dimethylamino)n-propylcarbamate by reacting n-propyl chloroformate in an aliphatic
(Cι-Gs)-alcohol.
By using the process of the present invention, it is possible to operate in a wide range of temperatures achieving very high yields. The fact that this reaction proceeds in such high yields is surprising since the alcohol would be expected to react with the n-propyl chloroformate especially in the presence of an acid acceptor like the 3-(dimethylamino)n-propylamine or n-propyl-3-
(dimethylamino)n-propylcarbamate itself, (see for example Houben-Weyl, 4th ed., (1983),
E4, page 68). However, in terms of the n-propyl chloroformate, a yield of 95% can be obtained by using this process and yields based on the amine can be even higher (up to 97%).
As one would infer, the present invention provides high yields of n-propyl-3- (dimethylamino)n-propylcarbamate compared with processes carried out in inert solvents or water (see DE 16 43 040, DE1 567 169, GB 1 212 708, 2 V 68 5172) or other standard carbamate processes (e.g. Houben-Weyl, 4th ed., (1983), 8, p. 138ff and E4, p.149ff).
An additional advantage of the process of the invention is that no additional acid acceptor is required.
Another advantage is that the reaction can be carried out in a wide range of temperatures from -20°C up to the boiling point of the alcohol and even higher, in general up to 200°G
Preferred temperature is about -20°C to about 110°C, especially preferred temperature is about -20°C to about 97°C. These temperatures and therefore reaction speeds are generally significantly higher than in other processes using only inert solvents, water or mixtures thereof (e.g. Houben-Weyl, 4th ed., (1983), 8, p. 138ff and E4, p.149ff). Often selectivity tends to decrease when using higher temperatures and in the toluene example the degradation of n-propyl chloroformate increases significantly at temperatures higher than 65°Cgiving large amounts of carbon dioxide and n-propyl chloride. In other literature examples (see Houben-Weyl, 4th ed. 11/1, p. 985f and E4, p.153f) this degradation is the main reaction even at lower temperatures. It is surprising that in our process the yield in terms of both compounds can stay stable even at temperatures above 85°C and that there is generally very limited degradation of n-propyl-chloroformate.
Alcohols used according to the invention are (CrCs)-, preferably (G-Gt)- aliphatic alcohols. Further preferred alcohols are propanols, especially n-propanol, also in recycled form. It is also preferred to use mixtures of one or more of such alcohols with water or inert organic solvents or mixtures thereof, preferably up to 30% by weight. Examples of inert organic solvents include toluene and ethers, e.g. THF or methyl t-butyl ether. For the process of the invention, reagents can be used either stoechiometric or in a molar excess up to 50%, preferably up to 10%. The molar ratio of 3-(dimethylamino)n-propylamine to n-propyl chloroformate is in general 1 : 0.75-1.5, preferably 1 : 0.95-1.1.
The process of the present invention is economically and environmentally advantageous due to several other features.
Alcohols, like n-propanol are environmentally and technically unproblematic solvents compared to ethers or dichloromethane or other inert solvents. Redistilled alcohol can be used.
The reaction can be carried out at a high concentration.
The exothermity at the high reaction temperature can be easily controlled.
There is almost no gas evolution during reaction and there is no waste water.
The invention is illustrated in the following example. Example
3-(dimethylamino)n-propylamine (184.4g) was added dropwise to recycled n-propanol
(443.5g) at 20-40°C. N-propyl chloroformate (227.3g) was added dropwise over 30-40 minutes. The temperature rose quickly and the flask was easily cooled so that the temperature was maintained at 80-85°C. After distilling off the n-propanol (which is later reused) the residue is n-propyl-3-(dimethylamino)n-propylcarbamate hydrochloride in a yield of 97% based on the 3-(dimethylamino)n-propylamine. This is 4% higher than when the reaction is carried out using toluene.
The yield was 95% based on the n-propyl chloroformate which is at least 16% higher than when the reaction is carried out with toluene. Example for the toluene process: n-propyl chloroformate (180g) was added dropwise to toluene (650g) at 20-40°C.
3-(dimethylamino)n-propylamine (125g) was added dropwise over 30-40 minutes. The temperature rose quickly and the flask was cooled so that the temperature was maintained at 55-60°C The reaction mixture was cooled to 40-45°C and water was added. After phase separation the crude n-propyl-3-(dimethylamino)n-propylcarbamate solution was distilled to give n-propyl-3-(dimethylamino)n-propylcarbamate hydrochloride in a yield of 93% based on 3-(dimethylamino)n-propylamine.
The yield was 79% based on the n-propyl chloroformate.
Claims (1)
- Claims:1 A process for the preparation of an alkyl-N-(3-dimethylamino)alkylcarbamate which comprises reacting an alkyl-chloroformate in an aliphatic (G-Cs) alcohol or a mixture of one or more of such an alcohol with up to 30% by weight of water or inert organic solvents or mixtures thereof.2 A process according to claim 1 for the preparion of n-propyl 3-(dimethylamino)n- propylcarbamate by using n-propyl chloroformate.3 A process according to claim 2 in which n-propanol or recycled n-propanol is the solvent.4 A process according to claims 1 to 3 running the reaction in a temperature range from about -20°C to about 110°C.5 A process according to any of claims 1 to 4 where both reagents can be used either stoechiometric or in a molar excess up to 50%.6 A process according to any of claims 1 to 5 where n-propyl chloroformate is preferably used in a molar excess of up to 10%.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01110711.7 | 2001-05-03 | ||
EP01110711A EP1254894A1 (en) | 2001-05-03 | 2001-05-03 | Process for the preparation of propamocarb |
EP01113778.3 | 2001-06-06 | ||
EP01113778A EP1264824A1 (en) | 2001-06-06 | 2001-06-06 | Preparation of alkyl-N-(3-dimethylamino)alkylcarbamates |
PCT/EP2002/005456 WO2002090322A1 (en) | 2001-05-03 | 2002-04-18 | Process for the preparation of alkyl-n-(3-dimethylamino)alkylcarbamates |
Publications (2)
Publication Number | Publication Date |
---|---|
AU2002314078A1 true AU2002314078A1 (en) | 2003-05-01 |
AU2002314078B2 AU2002314078B2 (en) | 2007-01-11 |
Family
ID=26076565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU2002314078A Ceased AU2002314078B2 (en) | 2001-05-03 | 2002-04-18 | Process for the preparation of alkyl-N-(3-dimethylamino)alkylcarbamates |
Country Status (21)
Country | Link |
---|---|
US (1) | US6872847B2 (en) |
EP (1) | EP1383737B1 (en) |
JP (1) | JP4261915B2 (en) |
KR (1) | KR100867910B1 (en) |
CN (1) | CN1246305C (en) |
AT (1) | ATE386015T1 (en) |
AU (1) | AU2002314078B2 (en) |
BR (1) | BR0209410A (en) |
CA (1) | CA2443820C (en) |
CZ (1) | CZ299629B6 (en) |
DE (1) | DE60224998T2 (en) |
DK (1) | DK1383737T3 (en) |
ES (1) | ES2301649T3 (en) |
HU (1) | HUP0303821A3 (en) |
IL (2) | IL158015A0 (en) |
MX (1) | MXPA03010032A (en) |
PL (1) | PL203712B1 (en) |
PT (1) | PT1383737E (en) |
SK (1) | SK287055B6 (en) |
TW (1) | TWI247732B (en) |
WO (1) | WO2002090322A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101548682B (en) * | 2009-04-14 | 2012-07-25 | 陕西恒田化工有限公司 | New method for synthesizing propamocarb hydrochloride of 722g/l |
BR112019006239A2 (en) * | 2016-10-31 | 2019-06-18 | Eastman Chem Co | process for preparing propyl 3- (dimethylamino) propyl carbamate. |
CN108218745A (en) * | 2018-03-12 | 2018-06-29 | 浙江禾本科技有限公司 | A kind of propamocarb synthesizing formula and its synthetic method |
CN113563230B (en) * | 2020-08-24 | 2023-04-11 | 江苏禾本生化有限公司 | Preparation method of propamocarb hydrochloride technical |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL157191C (en) | 1966-12-17 | Schering Ag | PROCEDURE FOR PREPARING A PREPARATION WITH FUNGICIDE AND FUNGISTATIC ACTION. | |
DE4133516A1 (en) * | 1991-10-10 | 1993-04-15 | Bayer Ag | METHOD FOR PRODUCING N- (HYDROXYALKYL) -CARBAMID ACID ALKYL ESTERS |
-
2002
- 2002-04-18 PT PT02740612T patent/PT1383737E/en unknown
- 2002-04-18 BR BR0209410-0A patent/BR0209410A/en not_active Application Discontinuation
- 2002-04-18 ES ES02740612T patent/ES2301649T3/en not_active Expired - Lifetime
- 2002-04-18 WO PCT/EP2002/005456 patent/WO2002090322A1/en active IP Right Grant
- 2002-04-18 AU AU2002314078A patent/AU2002314078B2/en not_active Ceased
- 2002-04-18 MX MXPA03010032A patent/MXPA03010032A/en active IP Right Grant
- 2002-04-18 EP EP02740612A patent/EP1383737B1/en not_active Expired - Lifetime
- 2002-04-18 HU HU0303821A patent/HUP0303821A3/en unknown
- 2002-04-18 DK DK02740612T patent/DK1383737T3/en active
- 2002-04-18 CN CNB028093399A patent/CN1246305C/en not_active Expired - Lifetime
- 2002-04-18 KR KR1020037014063A patent/KR100867910B1/en active IP Right Grant
- 2002-04-18 PL PL366847A patent/PL203712B1/en not_active IP Right Cessation
- 2002-04-18 CZ CZ20033261A patent/CZ299629B6/en not_active IP Right Cessation
- 2002-04-18 AT AT02740612T patent/ATE386015T1/en active
- 2002-04-18 IL IL15801502A patent/IL158015A0/en unknown
- 2002-04-18 SK SK1477-2003A patent/SK287055B6/en not_active IP Right Cessation
- 2002-04-18 JP JP2002587402A patent/JP4261915B2/en not_active Expired - Lifetime
- 2002-04-18 DE DE60224998T patent/DE60224998T2/en not_active Expired - Lifetime
- 2002-04-18 CA CA002443820A patent/CA2443820C/en not_active Expired - Fee Related
- 2002-04-18 US US10/476,706 patent/US6872847B2/en not_active Expired - Lifetime
- 2002-04-24 TW TW091108426A patent/TWI247732B/en not_active IP Right Cessation
-
2003
- 2003-09-18 IL IL158015A patent/IL158015A/en unknown
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1383737B1 (en) | Process for the preparation of alkyl-n-(3-dimethylamino)alkylcarbamates | |
US20090018364A1 (en) | Method for nitrating isourea | |
AU2002314078A1 (en) | Process for the preparation of alkyl-N-(3-dimethylamino)alkylcarbamates | |
HU195763B (en) | Process for production of derivatives of nitrosubstituated benzotrifluorid | |
JP2009137955A (en) | IMPROVED PRODUCTION METHOD OF CYCLOALKYL AND HALOALKYL o-AMINOPHENYL KETONES | |
US4086246A (en) | Process for the preparation of carbamate derivatives | |
EP1264824A1 (en) | Preparation of alkyl-N-(3-dimethylamino)alkylcarbamates | |
US7339081B2 (en) | Route to prepare 4-bromo-1-oxypentafluorosulfanylbenzene | |
US11760737B2 (en) | Process for manufacturing 4-(2,2,3,3-tetrafluoropropyl)morpholine | |
US4247479A (en) | Process for the manufacture of aromatic amines from α, β-unsaturated cycloaliphatic ketoximes | |
US5922916A (en) | Process to chloroketoamines using carbamates | |
US4293702A (en) | Method for preparing 4-substituted-N-methylbenzothiazolone derivatives | |
EP1254894A1 (en) | Process for the preparation of propamocarb | |
US20010031753A1 (en) | Process for the preparation of substituted benzophenones | |
US3932508A (en) | Polyfluoromethylthio-substituted compounds | |
JP2007277232A (en) | Method of nitration | |
US4256888A (en) | Preparation of 2-chloropyrimidines | |
JP2852023B2 (en) | Method for producing 2-fluorocyclopropylamine sulfonate and its chemical compound 2-fluorocyclopropyl isocyanate | |
EP0591236A1 (en) | Process for the preparation of 5-(3-butyryl-2,4,6-trimethyl)-2-(1-(ethoxyimino)propyl)-3-hydroxycyclohex-2-en-1-one. | |
MXPA98002594A (en) | Procedure for preparing chlorocetoamins with the use of carbama | |
JPH0625122A (en) | Aniline derivative and its production | |
HU181460B (en) | Process for preparing halo-acylamide derivatives | |
JPH05230010A (en) | Production of p-chlorophenylcarbamic acid ester | |
JPS58180461A (en) | Preparation of m-nitrophenyl alkyl ether |