IL28661A - Process for the manufacture of n-carbamoyloxyphenylcarbamates - Google Patents

Description

Process for the manufacture of oxy carbamates The present invention is concerned with a new which is simple to carry out for the manufacture of of the general formula in which and are identical or different and each represents a or branched aliphatic hydrocarbon group that may be substituted by furyl or represents a aromatic which is unsubstituted or may be substituted by aliphatic hydrocarbon or aromatic group which may be substituted by one or more subatitutoats selected from halogen atoms and alkoxy and alkylthio and may also each represent a hydrogen atom or also together with the adjacent nitrogen atom represent a non aromatic cyclic group that may contain at further nitrogen oxygen and and R5 each represents a hydrogen atom or a or branched aliphatic hydrocarbon Carbamates which correspond to the general formula indicated have already been proposed as materials for combatting The manufacture of such compounds is as a rule carried out by reacting with isocyanates or carbamic acid These processes however suffer from disadvantages which render the manufacture of the desired carbamates more or less difficult at times even Thus the reaction of the with isocyanates naturally only permits the manufacture of products which one of the two symbols and in the general formula given above represents hydrogen that is compounds which are monosubstituted in the carbamoyl Furthermore it is preferable to carry out this reaction und er anhydrous conditions in order to avoid decomposition of the If on the other the manufacture of compounds is a further reaction of the monosubstituted compounds with alkylating reagents is and this frequently does not take place with the formation of a single product but can lead to the formation of a for example to an alkylation at the other nitrogen atom represents The second process mentioned on the other admittedly permits the manufacture of both compounds which are monosubstituted and compounds which are disubstltuted in the carbamoyl In this the starting materials are carbamic acid chlorides which have to be The presented compounds may he prepared from the esters esters the general formula and For the different compounds R and the amines are listed R Ethyl Methyl Ethyl Methyl Ethyl Ethyl Ethyl Dlethylaralne or Ethyl Ethyl Methylaraine Methyl Ethyl Methyl Cyclohexylamlne Ethyl Cyc lohexy 26 i Cyclohexylamlne Cyclohexylamlne Butyl Cyclohex Ethyl Methyl Ethyl Ethyl luormethylanillne luormethylanillne h lamlne Cyclohexylamlne Cyclohexylamlne Methyl Aniline Ethyl Aniline Aniline Isopropyl line Aniline line Methyl Ethyl p ho or Ethyl amine Methyl amine R Ethyl Methyl Me thy Methyl Methyl thy Ethyl Ethylamine Isopropylamine Ethylamine Isopropylamine Isopropyl Ethylamine Isopropyl Isopropylamine Isopropyl Isopropyl Isopropyl Cy σ lohexy Ethylamine hyl Methyl Ethyl Ethylamine Ethyl Isopropylamine Ethyl te lamine Ethyl tert Methyl tert amine Isopropyl thy c Ethyl lamine Ethyl R Methyl Allylamine Ethyl All lamine Methyl Methyl Methyl Ethyl Ethyl Ethyl Methyl Methyl lanlline Methyl lamine Ethyl Methyl Methyl Methyl Ethyl Ethyl Ethyl Methyl Ethyl Methyl Ethyl lamine Allyl Ethylamine Allyl Allyl Allyl Allyl Allyl Aniline Allyl Ethyl Methyl or Methyl l Neopent lamine Ethyl Neopent Methyl Ethyl or Isopropyl Methyl Fu furylamine Phenyl Methylamine Phenyl Ethylamine hylphenyl Me thylamine Phenyl lamine Phenyl ex lamine Eth lamine Cyelo ylamine Phenyl Butylamine Phenyl I and Isopropyl or Ethyl luidlne or luidlne luidlne toluidlne Isopropyl or h Methyl or luidlne Methyl h or Allyl thiamine Fluor Allyl Allyl Allyl Allyl Allyl Allyl or to Allyl or o Allyl hy line or Ethyl or uidlne Isopropyl or N Dime thy to luidlne Allyl thy or o luidlne Allyl or Methyl Ammoniak The present invention provides a process for the manufacture of of the general formula given which comprises reacting an thane of the general formula 4e or a salt with phosgene presence of an amine of the general formula in the formula and have the meanings given represents a hydrogen atom or a or branched aliphatic hydrocarbon group and X represents a hydrogen a valent or en ammonium or The process of the present invention makes possible to manufacture the desired products under conditions which are easily realised a single process stage starting from and readily available cheap starting the reaction according to theprocess 4f of tbe present invention produces hardly any as for example carbonic acid but instead almost exclusively produces the desired which could not have been The process products are at the same time produced in a very good yield and in a high degree of The process according the present invention is explained by the following reaction sence of The symbols Rg and X in this equation have meanings given As starting materials for the process according to the present there may be used urethanes which for derived from primary secondary aliphatic as well as eyeloaliphatie or alcohols and In these alcohols may especially be for butyl and The salts of the which may also used as starting materials can fee manufactured in a manner known per se from the b action with metal hydroxides aqueous ammonia secondary tertiary As secondary or tertiary or which may if desired be of the general formula there be for the aniline isobutylamine fhese amines in an appropriate excess if also be used as and especially if as acid for example alkali for example sodium or for example The reaction according to the process of the present invention is preferably carried out in the presence of organic Hydrocarbons which may be ortionally orinated and and ethers such as ethyl acetonltrile and dioxan for proved to be suitable as such The reaction preferably takes place at room temperature or at an elevated temperature to but can occasionally even be carried out at temperature around The reaction mixture is worked up in a manner which known per s by either filtering off the salts which may have separated out or dissolving them by adding a little and then separating off the organic if desired drying and iltering and removing the solvent under reduced is frequently possible to allow the reaction products to separate out from the organic phase in a crystalline form by diluting the organic phase with ice and filtering them As has already been the defined according to the process of the present be manufactured in an industrially easi ly carried out and efficient surprisingly free of also in a very The obtainable according to the process of the present invention are generally colourless crystalline The products the proeess possess especially herbicidal properties and are inter suitable for use as materials for combatting According to a modification of the process of the present phosgene can first be reacted with as defined or with a salt if desired in the presence of an binding to form the correspondin chloroformate ester which is then reacted with an amine of the general formula as defined i desired without prior If the intermediate chloroformate ester can also be before reacting it following Examples illustrate the Example 1 g phosgene were dissolved in 40 ml A solution of g of g of and g of carbamate in 100 ml of dioxan was added while to the phosgene solution whilst cooling to 30 After cooling the mixture was poured ice The oil which first separated crystallized trituration with pure was purified by with a little g of the theoretical Melting point 139 to Example 2 Manufacture of A solution g of and g of in 50 ml of dioxan was added dropwise at 20 to to a solution of g of phosgene in 50 ml of while The mixture was then under reflux for 90 minutes poured into iee water after the carbamate was extracted with and the ethereal solution was washed with dilute sodium solution and ice water and was means of After evaporation the ether the carbamate crystallised on the addition of petroleum ethe g o the theoretical point 103 to fdllowing for can be manufactured according to the process of the present C carbamate 147 carbamate 138 carbamate o 10 carbamoylox 11 phenyl 16 C 17 hylcarbainoylox 18 carbamate 25 24 25 carbamoylox 26 IT 27 carbamoylox 28 29 of Physical constant 30 C 31 C carbamate l carbamate methyl C ylp C 5 carbamate 44 carbamate Compound Ox Compound Physical constan 58 59 60 61 of Compound constant 63 66 carbamoylo Ο 69 70 71 72 7 ccaarrbbaamaooyy 163 75 C 76 C 78 Compound l car 93 carbamoylox 95 Met carbamoylox lox l 97 98 99 100 P of Physical constant 3 but carbamate Et ft carbamate 3 A carba C C 114 ft 115 carbamate v 2 carbamate V Compound Physical constant 122 ca 124 125 me C C carbamate 127 p C C 30 131 isopropylca carbamate ylp carbamate 134 mo hen 1 t of ZV me 3 h carbama ound Physical co stant h carbamate 161 met 164 165 insufficientOCRQuality

Claims (1)

1. What vie A process for the manufacture of carbamate of the general formula in and each represents a or branched aliphatic hydrocarbon group that may be substituted by a or represents a aromatic is may be o nsubstituted o hydrocarbon group or hich may be substituted one or more substituents selected from halogen atoms and alkoxy may also each represent a hydrogen or also together with the nitrogen represent a non arofflatic cyclic group that ma contain at least one further nitrogen oxygen and and each represents a hydrogen atom or a or branched aliphatic hydrocarbon which reacting an d of the general or a salt with phosgene in the presence of a amine of the general formula i R and have the meanings given represents a hydrogen or a or branched aliphatic hydrocarbon group and represents a hydrogen monovalent or an or group A process as claimed in Claim wherein the reaction carried in the presence of an organic A process as claimed in Claim wherein the organic solvent is an optionally chlorinated carbon or is an or A process as claimed in any one of 1 to the reaction is carried out in the presence of an A process as claimed in any one of 1 to wherein the reaction is carried out a temperature o within the range of from about 0 to A process as claimed in Claim and conducted substantially as described in any one of o to 3 An whenever made by by process claimed in any one of insufficientOCRQuality