IL44709A - Preparation of esters of thiocarbamic acids - Google Patents

Preparation of esters of thiocarbamic acids

Info

Publication number
IL44709A
IL44709A IL44709A IL4470974A IL44709A IL 44709 A IL44709 A IL 44709A IL 44709 A IL44709 A IL 44709A IL 4470974 A IL4470974 A IL 4470974A IL 44709 A IL44709 A IL 44709A
Authority
IL
Israel
Prior art keywords
mercaptan
carbamyl chloride
aqueous solution
thiocarbamic
inclusive
Prior art date
Application number
IL44709A
Other versions
IL44709A0 (en
Original Assignee
Stauffer Chemical Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Stauffer Chemical Co filed Critical Stauffer Chemical Co
Publication of IL44709A0 publication Critical patent/IL44709A0/en
Publication of IL44709A publication Critical patent/IL44709A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Preparation of esters of thiocarbamic acide STAUFFER CHEMICAL COMPANY C. 42324 BACKGROUND OF THE INVENTION Field of Invention This invention relates to a novel method of preparing members of the class of compounds known as thiocarbama es. More particularly, this invention relates to the method of preparing esters of thiocarbamic acids by the reaction of an appropriate carbamyl chloride and requisite mercaptan in the presence of an aqueous solution of a caustic agent.
The general reaction scheme can be represented as follows : R, R^ and R2 are defined hereinafter.
Description of Prior Art The prior art contains many' various procedures for preparing and obtaining members of the class thiocarbamates.
The instant process includes certain preferred and desired advantages which will become apparent throughout the description to follow.
The esters of thiocarbamic acids are useful for a number of purposes, including use as herbicides. Some are effective for inhibiting the growth of micro-organisms such as bacteria. Others are valuable as insecticides. Therefore, the preparation of this class of compounds is desirable. Heretofore, such esters have been difficult to prepare because the preparatio require reagents, such as phosgene, which are difficult to handle or to employ reagents which leave residue problems and cause contamination.
U.S. Patent 2,983,747 employs zinc chloride as a catalyst in the direct reaction of carbamyl chloride with mer-captans to produce various thiocarbamic esters. The reaction can be conducted without the use of a solvent, however, a solvent inert to the catalyst, such as an organic solvent, must be used if a solvent is employed.
U.S. P.atent 2,913,327 teaches the preparation of the sodium salt of a mercaptan followed by reaction with a carbamyl chloride in the presence of a solvent. The use of the sodium salt of the mercaptan causes problems of filtration and solids handling. The use of a solvent involves the reduction of reactor throughput, as well as the solvent recovery which can be a problem. Hydrogen is evolved when making the sodium salt of the mercaptan, this causes a further disposal problem.
Another process is the reaction of the mercaptan with the carbamyl chloride in the presence of an acid binding agent such as pyridine. These agents are toxic, expensive and pose difficult recovery problems. The value of the hydrogen chloride is lost.
Another process for preparing esters of thiocarbamic acids' is the reaction of an appropriate chlorothioformate and secondary or primary amine in the presence of an inert solvent such as diethyl ether or n-pentane, and in the presence of a suitable hydrogen chloride acceptor, including the tertiary U.S. Patent 3,133,947 describes the preparation oHP esters of thiocarbamic acids by a process comprising reacting a secondary or primary amine with carbonyl sulfide in the presence of a basic material which may be any amine, including a tertiary amine, and thereafter reacting the intermediate with an organic sulfate, such as dialkyl sulfate or diallyl sulfate. This process is unfavorable because of the special gas handling equipment required for the carbonyl sulfide addition. Further, alkyl sulfate values are lost which add to the expense of the overall process.
SUMMARY OF INVENTION It is the object of this invention to provide a process for the preparation of esters of thiocarbamic acids in high yields with convenient starting materials which are easy to handl in a novel reaction system heretofore unknown.
It is a further object of this invention, as will become apparent during the course of the description, that undesirable gases, such as carbonyl sulfide, are not required.
Further, tertiary organic amines as acid acceptors or catalysts are not required.
This invention, therefore, relates to the method of preparing esters of thiocarbamic acids by the reaction of an appropriate carbamyl chloride and requisite mercaptan in the presence of an aqueous solution of a caustic agent. The above and related objects are accomplished by a process which may be represented by the following typical equation: wherein R, R^ and R2 are as defined hereinafter.
Certain side reactions may take place simultaneously with the above-mentioned re'action. These side reactions may use up large amounts of the starting materials with a consequent lowering of the yield of the desired thiocarbamic ester. The control of the desired reaction is therefore very important, so that the amount of the undesirable by-products produced therein will be minimized. ' The steps of the process of this invention comprise reacting an appropriate carbamyl chloride with a selected mercap-tan in the presence of an aqueous caustic solution. The general procedure comprises adding the requisite mer aptan to an aqueous caustic, solution to form the corresponding salt in situ . Thereafter, the appropriate carbamyl chloride is mixed with the salt-containing caustic solution. The reaction vessel is maintained at the desired temperature for the necessary time to achieve efficient and economical yields of the corresponding ester of the thiocarbamic acid. Also contemplated within the steps of thi process is the addition of a mixture of the mercaptan and the carbamyl chloride to the aqueous caustic solution. This latter means of addition is preferred when the mercaptan forms a solid in the aqueous caustic solution, for example, in the case of benzyl mercaptan. The formation of solid interferes . with agitation and rapid reaction of the mercaptan salt formed in the aqueo caustic solution and the carbamyl chloride.
Generally, it has been found that any raercaptan an^i any carbamyl chloride can be used in the instant process, thereby the process is applicable to prepare esters of thiocarbamates, for example, of the formula where the symbols R-^ and R2 may independently represent groups selected from alkyl, for example, having from 1 to 12 carbon - atoms, inclusive; alkenyl, for example, having at least 1 double bond and from 2 to 8 carbon atoms, inclusive; haloalkyl, for example, having from 1 to 12 carbon atoms, inclusive, and halo is chloro, fluoro, or bromo; cyano-substituted alkyl, for example, having from 2 to 6 carbon atoms, inclusive; alkynyl, having at least one triple bond and from 3 to 6 carbon atoms, inclusive, for example, propargyl, isobutynyl, and the like; cyclohexenyl; haloalkenyl, for example, having from 2 to 8 carbo atoms, inclusive, and halo is chloro, fluoro or bromo; benzyl ; substituted-benzyl, in which the substituents are, for example, chloro, lower alkoxy having 1 to 4 carbon atoms, inclusive, cyano, nitro and trifluoromethyl; haloalkoxy, for example, having 1 to 8 carbon atoms, inclusive, and halo is chloro, fluoro or bromo; alkoxy, for example, having 1 to 8 carbon atoms, alkenyloxy, for example, having at least 1 double bond and from 2 to 8 carbon atoms, inclusive; nitroalkoxy, for example, having 1 to 6 carbon atoms, inclusive; phenyl ; substituted-phenyl, in which the substituents are, for example, chloro, bromo, nitro, cyano, alkoxy having 1 to 4 carbon atoms, inclusive, phenyl and the like; phenoxy-substituted alkyl, for example, in v;hich alkyl has from 1 to 4 carbon atoms, inclusive; naphthyl; furfuryl, tetra-hydrofurfuryl; cycloalkyl, for example, having from 3 to 7 carbon atoms, inclusive; heterocyclic oxygen, nitrogen or sulfur-containing ring groups, for example, pyridyl, thienyl, furyl, pyranyl, pyrimidinyl, indolyl, quinolyl, isothiazolyl, piperidyl, piperazinyl, morpholinyl and the like; alkyl-substituted pyridyl, for example, where alkyl has from 1 to 4 carbon atoms, inclusive. and taken together with the nitrogen represent heterocyclic groups, e.g., pyrryl, pyrrolidyl, pyrazolyl, pyra-20linyl, piperidinyl, imidozolyl, indolyl, -methyl-indolyl, aziridinyl, carbazolyl, morpholinyl, 3-azabicyclo- [3.2.2 ]nonanyl-poly alk leneimine , having 3 to 6 carbon atoms, inclusive, alkyl-substituted piperidine, for example, 5-ethyl-2-methyl piperidine.
R represents alkyl, for example, having 1 to 12 carbon inclusive ; haloalkyl, preferably chloro or bromo-substituted alkylthioalkylene , for example, having a from 2 to 10 carbon atoms, inclusive; alkoxyalkylene , for example, having a total of from 2 to 10 carbon atoms, inclusive; cycloalkyl, for example, having 3 to 7 carbon atoms, inclusive;- alkenyl, for example, having at least 1 double bond and from 2 to 8 carbon atoms, inclusive; alkynyl, having at least one triple bond and from 3 to 6 carbon atoms, inclusive, for example, isobutynyl 3-raethyl-butyn-(l)yl(3) ; ' phenyl; naphthyl; benzyl; d -alkyl benzyl, for example, in which the alkyl has 1 to 4 carbon atoms, inclusive; sub-phenyl wherein said substituents include alkoxy having 1 to 4 carbon atoms, inclusive, nitro, chloro, trifluoro, methyl, for example, 0-methoxy, m-butoxy, p-nitro, 3,4-dinitro, 2,4-dinitro; substituted-naphthyl, for example, wherein said substituents include alkoxy, nitro, chloro, bromo, trifluoromethyl; haloalkenyl, for example, in which alkenyl has 2 to 6 carbon atoms, inclusive, and halo is chloro, bromo, iodo or fluoro, for example, 2 ,3-dichloroallyl, 3 ,4 ,4-trifluoro-3-butenyl, 2-bromoallyl, and the like; cyclohexenyl; substituted-benzyl, wherein the substituents for example, halo, chlorine, bromine, fluorine, methyl- p-methyl, o-methyl, 2 ,4-dimethyl, 2 ,6-dimethyl, 2,4-di- chloro, 3 ,4-dichloro, ar,ar,ar-trichloro, 5-chloro-2- methoxy, nitro; carboalkoxalkyl, for example, having from 2 to 8 carbon atoms, inclusive; phenyl thioethyl; phenyl oxyethyl; pyrimidyl; pyridyl; indazolyl; quinolyl; isoquinolyl; furyl; dibenzofuryl.
The present invention may be practiced in a batch or batch-like form or i a continuous or continuous-like form.
When the invention is practiced in a manner resembling a batch process, all the various liquids and various reactants will be brought together and various steps determined by the proper time sequence into a single body of liquid. The batch process may be altered by using suitable reactors such that a continuous or continuous-like form of the process is achieved. In the continuous form of the inventive process, agitation of the reacting phases may continuously be practiced at a proper rate to continuously form a suitable mixing of droplets of the two phases in such a manner that a continuously supplied portion of the carbamy chloride is added to a reactor in which the aqueous caustic concentration can be adjusted and the appropriate heat applied to achieve the desired reaction. Within the continuous system, the proper rate for reaction may be obtained by selecting the appropriate conditions. Both the batch and continuous aspects of the present invention are highly desirable, and choice there between will rest solely with the desired manufacturing conditions.
The reaction vessel consists entirely of non-corrosive materials, such as mild-steel, which will not interfere with the principle reaction.
The conditions of the reaction can be varied rather extensively without having appreciable effect on the yield or quality of the product. The temperature of the reaction can range from about 10 to about 100°C. and preferably from about 20 to about 80°C. More preferably, the reaction is to be performed at from about 40 to about 60°C. Within the temperature limits specified herein, it is found that esters of thiocarbamic acids can be prepared and that the undesirable by-product of the corresponding urea will be minimized. The selected temperature also determines the rate of the reaction; that is, the time required to economically and feasibly arrive at the product with a negligible amount of carbamyl chloride remaining. The reaction time, therefore, will depend upon several interacting factors, such as temperature and degree of agitation. These parameters will be developed hereinafter.
The ratio of reactants employed in the instant process can vary widely. However, with economic feasibility as a basis, the ratio of mercaptan (RSH) to carbamyl chloride (R, R^NCOCl) must be at least about 1.1. The preferred ratio of mercaptar^to carbamyl chloride is at least 1.2. That is an excess of mercap- tan is used. This is advantageous in the case that the carbamyl chloride is expensive.
The ratio of caustic agent to mercaptan is at least 0.5, however, the preferred ratio of caustic agent to mercaptan is at least 1.0. The most preferred ratio of caustic agent to mercaptan is at least 1.5. That is, in the most preferred form, this process is carried out with an excess of caustic agent.
By caustic agent, it is meant any inorganic material which will sufficiently produce hydroxy1 ions in an aqueous solution to function in this process. The nature of the caustic agent must produce sufficient alkalinity in an aqueous solution to inhibit or suppress the hydrolysis of the mercaptide RS ion to the mercaptan according to the equation: RS~ + 1^0 ^ RSH + 0H~ <ς The caustic agents contemplated for use in this process include among others, sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, strontium hydroxide, calcium hydroxide, and the like, and mixtures thereof. The caustic agent is supplied to the reaction scheme as an aqueous solution which can range from 10% to 50% and higher, such that the solutio is liquid. For example, when using sodium hydroxide, the preferred range of caustic solution is 20% to 507o.
An important aspect of the process is to provide adequate agitation. The reaction will proceed slowly with little or no agitation. There will be various side reactions occurring which produce undesirable by-products or no reaction will occur and unreacted starting material will remain. Therefore, as cT preferred step in the process, there must be an adequate means of agitation to form high surface area of the two liquid phases in the reaction vessel. Adequate agitation is essential to achieve rapid reaction and arrive at economic yields. Present in the reaction vessel are -two phases, an organic phase or carbamyl chloride phase and aqueous phase containing the mercap-tan and caustic agent. Adequate means of agitation can be accomplished, for example, by use of high speed stirrers, baffle plate within the reaction flask, together with high speed stirring, rapid circulation through mixing o^ turbulence columns and the like .
Upon completion of the process reaction, the thiocar-bamate ester produced from the reaction remains in the organic phase. There may be some solid salt formation which can be removed easily by addition of water to dissolve the salt. The salt may be formed during the reaction. With two phases present in the reaction vessel, the two phases can be separated easily. The organic phase is dried by conventional means and the pure thiocarbamate ester obtained therefrom. Further purification can be accomplished by distillation. The product can be stripped of residual water and volatile components by purging with argon or nitrogen while heating.
Specific examples are set forth below showing the preparation of the esters of this invention. These examples are present herein for illustrative purposes only, and are not to be interpreted as imposing any limitations on the scope of the invention herein described, other than as set forth in the appended claims.
EXAMPLES General Procedure The general procedure used in the following experiments was as follows. An aqueous solution of sodium hydroxide was placed in an agitation flas-k equipped with a stirrer. The appropriate mere aptan was added to the aqueous solution. To this mixture was added the requisite carbamyl chloride while maintaining the flask and its contents at the indicated temperature. At the end of the experiment water was added to dissolve any precipitated salts and the organic layer/ containing the thiocarbamic acid ester was separated. The organic layer was either heated under a vacuum or purged with nitrogen while heating to remove residual water and mercaptan. The conditions, reactants and results are summarized and reported in the following table.
The results are area per cent from gas chromatography analysis of the- material. In several instances, a weight per cent purity also was determined and found to agree within experimental error to the gas chromatographic analysis.
TABLE Ratio Cone. Na NaOH/RSH % Preparation- of S-ethyl hexahydro-lH-azepine-l-carbothioate; RSH R-j^ COCl = hexahydro-lH-azepine-1 carbamyl chloride. 1 28-35 1.2 1 20 2 28-35 1.2 1 20 3 45 1.2 1 33 4 45-47 1.2 1.6 50 5 44-50 1.2 1.6 50 6 50 1.2 1.6 50 7 60 1.2 1.6 50 60 1.2 1.6 50 I-1 I 8 55 1.2 1.6 50 55 1.2 1.6 50 B. Prep 9a 50-60 1.2 1.6 50 Reaction conditions the same as Experiment #9 except that a mix chloride was added to 50% NaOH solution.
Ratio Ratio Cone. ment Cone. N Experi N Number Temp. °C. RSH/RJRQNCOCI NaOH/R SSHH %% Preparation of S-propyl butylethylthiocarbamate; RSH = n-prop R-,R NC0C1 = butylethylcarbamyl chloride. 10 55 1.2 1.6 50 Preparation of S-ethyl dipropylthiocarbamate ; RSH = ethyl mer R1R2NC0C1 = dipropylcarbamyl chloride. 11 50-55 1.2 1.6 50 50-55 1.2 1.6 50 50-55 1.2 1.6 50 12* 50 1.2 1.6 50 13** 48-52 1.2 1.6 50 1.2 1.6 50 1.2 1.6 50 * Conditions substantially the same as Experiment #11, excep ** Conditions substantially the same as Experiment #12, excep agitation employed.
As can be seen from the Table, especially with referehc to Experiments 1 and 2 performed under similar conditions except for the reaction time, substantial amount of thiocarba ic ester can be produced, but the longer reaction time produces undesirable by-products. However, by-product formation can be substantially reduced and the temperature allowed to increase if the ratio of caustic agent to mercaptan is increased, as seen in comparing Experiment 2 and 8 in the Table.
Many modifications and variations of this invention may be made without departing from t^he spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

Claims (16)

WHAT IS CLAIMED IS:
1. The process of preparing esters of thiocarbamic acids which comprises a) reacting a carbamyl chloride with a mercaptan in the presence of an aqueous solution of a caustic agent; b) separating the organic and aqueous phases; and c) recovery of the thiocarbamic acid ester from the organic phase.-
2. The process of reacting a carbamyl chloride with a mercaptan which comprises reacting the compounds in an aqueous solution of a caustic agent at a temperature of from about 10°C. to about 100°C. in the presence of an aqueous solution of a cuastic agent and recovering therefrom the thiocarbamic ester.
3. The process according to Claim 2 in which the ratio of mercaptan to carbamyl chloride is at least 1.1:1, and the ratio of mercaptan to caustic agent is at least 1:0.5.
4. The process according to Claim 3 in which the ratio of mercaptan to carbamyl chloride is at least 1.2:1, and the ratio of mercaptan to caustic agent is at least 1:1.
5. The process of reacting a carbamyl chloride with a mercaptan which comprises reacting with agitation the compounds in an aqueous solution of a caustic agent at a temperature of from about 10°C. to about 100°C. in the presence of an aqueous solution of excess caustic agent and recovering therefrom the thiocarbamic ester.
6. The process according to Claim 5 in which said caustic agent is sodium hydroxide. *
7. The process according to Claim 6 in which the rati of mercaptan to carbamyl chloride is at least 1.2:1, and the ratio of mercaptan to caustic agent is at least 1:1.1.
8. The process for preparing thiocarbamic esters by reacting an aqueous solution of a carbamyl chloride of the formu in which R-^ and R2 taken together with the nitrogen represent polyalkyleneimine having 2 to 6 carbon atoms, inclusive; and a mercaptan of the formula RSH in which R is alkyl having 1 to 12 carbon atoms, inclusive, which comprises reacting the said compounds in an aqueous solutio of excess caustic based upon the mercaptan at a temperature of from'..'-'about 10°C. to about 100°C. with agitation and recovering therefrom the thiocarbamic ester.
9. The process for preparing thiocarbamic esters by reacting an aqueous solution of a carbamyl chloride of the formul in which R^ and R2 are independently alkyl having from 1 to 12 carbon atoms, inclusive, and RSH in which R is alkyl having 1 to 12 carbon atoms, inclusive, which comprises reacting the said compounds in an aqueous solution of excess caustic based upon the mercaptan at a temperature of from about 10°C. to about 100°C. with agitation and recovering there
10. The process for preparing thiocarbamic esters by reacting an aqueous solution of a carbamyl chloride of the formul in which R^ and R2 are independently alkyl having from 1 to 12 carbon atoms, inclusive; and RSH in which R is benzyl, which comprises reacting the said compounds in an aqueous solution of excess caustic based upon the mercaptan at a temperature of from about 10°C. to about 100°C. with agitatio and recovering therefrom the thiocarbamic ester.
11. The process for preparing thiocarbamic esters by reacting an aqueous solution of a carbamyl chloride of the formula in which R^ and R2 independently are alkyl having from 1 to 12 carbon atoms, inclusive; and RSH in which R is haloalkenyl having at least one double bond and 2 to 6 carbon atoms, inclusive, and halo is selected from chloro, bromo, iodo and fluoro; which comprises reacting the said compounds in an aqueous solution of excess caustic based upon the mercaptan at a temperature of from about 10°C. to about 100°C. with agitation and recovering therefrom the thiocarbamic ester. * f
12. The process for preparing thiocarbamic esters by reacting a carbamyl chloride of the formula in which R^ and R2 are independently alkyl having from 1 to 12 carbon atoms, inclusive; and RSH in which R is substituted benzyl in which the substituents are selected from chloro, lower alkoxy having 1 to 4 carbon atoms, inclusive, intro, chloro, trifluoromethyl, which comprises react ing said compounds in an aqueous solution of excess caustic base upon the mercaptan at a temperature of from about 10°C. to about 100°C. with agitation and recovering therefrom the thiocarbamic ester .
13. The process according to Claim 8 in which said carbamyl chloride is nexahydro-lH-azepine-1 carbamyl chloride and said mercaptan is ethyl mercaptan.
14. The process according to Claim 9 in which said carbamyl chloride is butylethyl carbamyl chloride and said mercaptan is n-propyl mercaptan.
15. The process according to Claim 9 in which said carbamyl chloride is dipropyl carbamyl chloride and said mercaptan is ethyl mercaptan.
16. The process according to Claim 10 in which said carbamyl chloride is di -n-propyl carbamyl chloride. For Ihe/Z plicants ttt REINWOLD OHN AND PARTNERS
IL44709A 1973-04-26 1974-04-24 Preparation of esters of thiocarbamic acids IL44709A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00354591A US3836524A (en) 1973-04-26 1973-04-26 Preparation of esters of thiocarbamic acids

Publications (2)

Publication Number Publication Date
IL44709A0 IL44709A0 (en) 1974-06-30
IL44709A true IL44709A (en) 1977-05-31

Family

ID=23394048

Family Applications (1)

Application Number Title Priority Date Filing Date
IL44709A IL44709A (en) 1973-04-26 1974-04-24 Preparation of esters of thiocarbamic acids

Country Status (25)

Country Link
US (1) US3836524A (en)
JP (1) JPS5821620B2 (en)
AR (1) AR214703A1 (en)
BE (1) BE814159A (en)
BR (1) BR7402737A (en)
CA (1) CA1040200A (en)
CH (1) CH592619A5 (en)
CS (1) CS175475B2 (en)
DD (1) DD112995A5 (en)
DE (1) DE2418592C2 (en)
EG (1) EG11052A (en)
ES (1) ES425672A1 (en)
FR (1) FR2227267B1 (en)
GB (1) GB1462974A (en)
HU (1) HU170213B (en)
IL (1) IL44709A (en)
IN (1) IN139496B (en)
IT (1) IT1008474B (en)
NL (1) NL7405594A (en)
PH (1) PH12412A (en)
PL (1) PL91624B1 (en)
RO (1) RO66489A (en)
SU (1) SU685147A3 (en)
YU (1) YU114774A (en)
ZA (1) ZA742654B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4919841U (en) * 1972-05-26 1974-02-20
US4213915A (en) * 1976-06-30 1980-07-22 Ppg Industries, Inc. N-Halo-alkyl thiolcarbamates and N-alkenyl thiolcarbamates
US4311649A (en) * 1980-11-28 1982-01-19 The United States Of America As Represented By The Secretary Of The Navy N,N-Bis(2-fluoro-2,2-dinitroethyl)carbamate esters
EP2052606A1 (en) 2007-10-24 2009-04-29 Bayer CropScience AG Herbicide combination
DE102008037620A1 (en) 2008-08-14 2010-02-18 Bayer Crop Science Ag Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides
JP6027009B2 (en) 2010-10-15 2016-11-16 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ Use of ALS inhibitor herbicides for controlling undesirable vegetation in ALS inhibitor herbicide-tolerant beta-bulcalis plants
UA117447C2 (en) 2011-05-04 2018-08-10 Байєр Інтеллектуал Проперті Гмбх Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant brassica, such as b. napus, plants
DK2931034T4 (en) 2012-12-13 2022-07-18 Bayer Cropscience Ag USE OF ALS INHIBITOR HERBICIDES TO CONTROL UNDESIRABLE VEGETATION IN ALS INHIBITOR HERBICIDE TOLERANT BETA VULGARIS PLANTS
KR20180067703A (en) 2013-03-05 2018-06-20 아사히 가세이 케미칼즈 가부시키가이샤 Isothiocyanate production method, composition for transporting and storing n-substituted o-substituted thiocarbamate, and isothiocyanate composition
CN105494384B (en) * 2015-12-28 2018-04-27 江苏傲伦达科技实业股份有限公司 A kind of Herbicidal combinations containing cyhalofop-butyl and prosulfocarb
CN118201483A (en) 2021-10-15 2024-06-14 科沃施种子欧洲股份两合公司 ALS inhibitor herbicide-tolerant sugar beet (Beta vulgaris) mutants
WO2025045998A1 (en) 2023-08-30 2025-03-06 Bayer Aktiengesellschaft Herbicide combinations

Also Published As

Publication number Publication date
FR2227267A1 (en) 1974-11-22
BE814159A (en) 1974-10-25
AR214703A1 (en) 1979-07-31
PH12412A (en) 1979-02-07
AU6823174A (en) 1975-10-30
SU685147A3 (en) 1979-09-05
DE2418592A1 (en) 1974-11-14
RO66489A (en) 1980-01-15
JPS5018418A (en) 1975-02-26
IL44709A0 (en) 1974-06-30
CS175475B2 (en) 1977-05-31
PL91624B1 (en) 1977-03-31
JPS5821620B2 (en) 1983-05-02
ZA742654B (en) 1975-04-30
BR7402737A (en) 1975-12-23
DE2418592C2 (en) 1982-06-03
IT1008474B (en) 1976-11-10
DD112995A5 (en) 1975-05-12
YU114774A (en) 1982-06-30
GB1462974A (en) 1977-01-26
IN139496B (en) 1976-06-26
FR2227267B1 (en) 1978-01-27
NL7405594A (en) 1974-10-29
ES425672A1 (en) 1976-11-16
US3836524A (en) 1974-09-17
CH592619A5 (en) 1977-10-31
HU170213B (en) 1977-04-28
CA1040200A (en) 1978-10-10
EG11052A (en) 1977-01-31

Similar Documents

Publication Publication Date Title
IL44709A (en) Preparation of esters of thiocarbamic acids
JPH026465A (en) Production of organic disulfide and polysulfide
US4424167A (en) Process for the preparation of 2,3-dichlorosulphonyl-acrylonitriles
US3752841A (en) Process for the preparation of carbamates of alkylthiolhydroxamates and intermediates
US2277325A (en) Sulphonyl halides
CA1113483A (en) Thiocarbamate preparation utilizing quarternary ammonium salt catalysts
US2449644A (en) Production of n.n dibutyl phenethylamine
JPS61249964A (en) Preparation of 3,4,5,6-tetrachloro-2-trichloromethylpyridinerich mixture
CN115043786B (en) Fluorination method of florfenicol intermediate
EP0039166B1 (en) Continuous process for the production of dichloroacetamides
US2572845A (en) Alkylthiosulfenyl dithiocarbamates and preparation thereof
SU921464A3 (en) Method of producing esters of thiocarbamic acid
JPH03176435A (en) Synthetic preparation of perfluoroalkyl- bromide
US4770820A (en) Process for the preparation of carbamoyl chlorides derived from secondary amines
US6187960B1 (en) Process for producing organic polysulfide compounds
JPH0465063B2 (en)
US4283338A (en) Process for producing O,O-dialkyl dithiophosphoric acid esters
EP0204848B1 (en) Preparation of symmetrical tetrachloropyridine from chlorinated beta - (trichloromethyl) pyridines employing a catalyst
DE69604878T2 (en) Manufacture of alkanesulfonamides with low residual ammonium impurities
SU1004365A1 (en) Process for producing naphthalenethioles
JP2870971B2 (en) Method for producing alkenylphenol
EP0156728B1 (en) Process for the preparation of thiocarbamates
JPH0253764A (en) Production of dithiobisphenol
JPS5946255A (en) Method for producing 2-alkoxymethylene-3,3-dialkoxypropanenitrile
SU1331860A1 (en) Method of producing 1-chloro-1-phenylethane