JPS6140256A - Manufacture of thiol carbamate ester - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention This invention is based on the following general formula f'I), [wherein R1 and R2 are independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms] or an alkenyl group having 2 to 6 carbon atoms, or an alkenyl group having 1 to 6 carbon atoms.
alkyl groups or alkenyl groups having 2 to 6 carbon atoms, which groups are mono- or poly-substituted with halogen, oxygen, sulfur and/or nitrogen; or R and R together is an optionally substituted group having 4 to 6 carbon atoms, ω-alkylene group; R and R are independently hydrogen or 1 to 4 carbon atoms;
alkyl groups (in some cases, polysubstituted by groups containing !su, ``oxygen'', sulfur □ and ``nitrogen'')
and R5 and R6 are both hydrogen; or R and R together form a chemical bond.

Depending on the meaning of R5 and R6, the esters produced by the process of this invention are S-alkylthiol carbamates (when R and R together constitute a chemical bond);
or S-alkylthiol carbamates (R5 and R6
are both hydrogen). Compounds of the former type are used in the industry of plastic (synthetic) materials for the production of polymeric substances and as intermediates for the production of plant protection agents, whereas compounds of the latter type are used for plant preservation in agriculture. Used as an active ingredient in compositions.

A widely used method for producing vinyl compounds is
It involves adding a substance containing mobile hydrogen to acetylene. The possibility of using this method was demonstrated by W. Reppe [Ann, 60
1 r81-138 (1956)], but alkenyl esters of thiol carbamic acids are not disclosed.

C, G, Overberger et al. (J, Org,
Chem, 27.

4331-4337 (1962)) were the first to study a method for producing 5-(1-alkenyl) esters of monothiocarbamic acids. The principle of these processes comprises the removal of previously prepared S-(β-chloroethyl) monothiocarbamate with potassium teyt-butoxide. Although this method gives good yields,
The expensive, corrosive, and toxic nature of the starting materials has prevented them from being widely used in practice.

In practice, S-alkylthiol carbamates of general formula (1) are obtained by reacting primary, secondary or tertiary ammonium salts or alkali metal salts of suitable thiolcarbamic acids with alkyl halides. Soviet patent specification shop 224.511 and 186,437:
German patent specifications A2,513,196 and 2,844,
305; Japanese patent specification point 75-76026.78-
25564.77-28832 and 77-746027
: and U.S. Patent Specifications A3,167.571 and 3
, 151.119).

German patent specification shop 2,212,766 and 2,117,
115, as well as US Pat. No. 4,066,081, the phosdan is reacted with an alkyl mercaptan and the resulting alkyl chlorothioformate is reacted with a secondary or tertiary amine.

S-alkylthiol carbamates can also be prepared by reacting carbamoyl chlorides with alkyl mercaptans (U.S. Pat.
2,983,747 and 2.913,327, and Spanish Patent Specification House 422.149).

According to German Patent Specification 42,703,106, dithiol carbamates are obtained by reacting dithiocarbamates with dimethyl sulfate and molecular iodine.

According to German Patent Specification A 2,461,876, S-alkyl esters are obtained via isomerization by heating 0-alkylthiocarbamates with dialkyl sulfates.

According to US Pat. No. 4,071,423, thiol carbamates are obtained in very high yields by radical addition of thiol carbamate salts to olefins.

All these methods require expensive starting materials or represent a serious burden on health and environmental protection.

Therefore, an object of the present invention is to provide a new and advantageous method for producing S-alkylthiol carbamates and S-alkenylthiol carbamates represented by general formula (1).

This invention solves the problem of the general formula (■) by the nucleophilic addition of a salt of a thiolcarbamate to a 1-alkyne, e.g. acetylene.
It is based on the knowledge that unsaturated compounds can be obtained. Furthermore, it is not essential to pre-prepare and isolate the thiol carbamate salt; the material can be prepared in situ from the reaction of a suitable amine with carbon monoxide and sulfur, or from the reaction of a suitable amine with carbon sulfide. It has now been recognized that O can be produced and reacted directly with alkynes.
It is based on the knowledge that S-alkylthiol carbamates of general formula (1) can be prepared by hydrogenation of alkenylthiol carbamates. until now,
Hydrogenation of S-alkenylthiol carbamates to the corresponding S-alkyl derivatives has not been reported.

Therefore, the present invention provides a method for producing a thiol carbamate ester represented by the following general formula (■), (wherein R1, R2, R3, R4, R5 and R have the above-mentioned meanings), comprising: a) A compound of the general formula (II), in which R1 and R2 have the meanings given above and Y is a primary, secondary or tertiary ammonium ion, or an alkali metal ion; or, b) an amine, sulfur, and carbon oxide represented by the general formula (m), in which R1 and R2 have the meanings given above; or C) a compound of the general formula CI[I], and a carbon oxide; Nyl sulfide; and the following general formula (mV), R-CmiC
-R' (IV) in which R5 and R4 have the meanings given above, and optionally J), R11R2+ R3 and R have the meanings given above and R and Together with R,
The present invention relates to a process characterized in that a compound of general formula (1) in which R5 and R6 are both hydrogen is produced by hydrogenating the product of general formula (I) obtained by forming a chemical bond.

According to variant a), a thiol carbamate salt of the general formula (...) and a suitable 1-alkyne are combined in a lower aliphatic alcohol, such as methanol, ethanol, n-furonol, isonoropanol, or n-1see- or ta
The reaction is carried out in a solution prepared with rt-butanol, preferably methanol, or in the presence of an inert solvent, such as tetrahydronerane. The reaction of this solution with a suitable alkyne is carried out at a pressure of 0.1 to 10 MPa.
It is carried out at a temperature of 00°C to 160°C for 2 to 10 hours.

A preferred embodiment of process variant a) of the invention comprises preparing as concentrated a solution as possible of the thiol carbamate salt of general formula (U). 30% by weight to achieve good yield
Concentrations above have proven to be very advantageous.

The conditions for variants b) and C) of this invention are similar.

The reaction temperature can vary over a wide range, from 25°C to 200°C.
The temperature is preferably 80°C to 160°C. There is no need to hold the temperature constant. That is, the amine, carbon monoxide and sulfur can be reacted at about 100° C., and for reaction with the alkyne, the reaction mixture can be cooled or heated depending on the reactivity of the alkyne.

Reaction time varies from 30 minutes to 30 minutes depending on the amount and reactivity of reactants.
It is 30 hours.

Generally, the order in which the reactants are added is not critical.

However, it is preferred to charge the required amount of amine and sulfur to the reactor, seal it and then fill it with acetylene, and finally adjust the pressure of carbon monoxide and acetylene. The reactants can be added batchwise or continuously.

The molar ratio of amine to sulfur can generally vary in the range from 5=1 to 1:5. Preferably an excess of sulfur is used in order to achieve as high a conversion of the amine as possible. - The molar ratio of carbon oxide to sulfur ranges from 1:1 to 3:1.

Finally, the molar ratio of alkyne to amine can be varied over a wide range (from about 1:2 to about 100:1; the required amount of lower alkyne, e.g. acetylene, increases the pressure in the reaction mixture from 0.1 to about 100:1. 5 MPa.

The reaction can be carried out in the presence or absence of a solvent.

Suitable solvents include lower alkanols such as methanol,
ethanol, guloΔnol, impronognol, and n-, iso+, tert- and 5ec-butanols, preferably methanol; aprotic polar solvents;
For example acetonitrile, benzonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide; inert solvents such as ethers, such as tetrahydrofuran, dioxane; acetone; and tertiary aliphatic amines, pyridine and their homologs; finally aromatic hydrocarbons. , chlorinated hydrocarbons, caldicic acids and esters of caldicic acids.

The reaction can in some cases be accomplished without solvent, ie in the melt.

During the synthesis of various alkenylthiol carbamates, a decrease in the rate of the vinylation reaction towards the end of the conversion is often observed. In this case, it is advantageous to alkylate the unconverted salt in a suitable manner in order to shorten the reaction time and achieve the highest possible availability of the amine. This method directly converts the prepared S-alkenyl ester into K
This is advantageous when converting to S-alkyl esters. That is, the S-vinyl ester is prepared by treating the incompletely converted reaction mixture with diethyl sulfate or ethyl chloride. The resulting mixture of S-alkenyl and S-alkyl compounds is then further processed.

In a final optional step of this invention, if desired) the obtained fcS-alkenyl ester of general formula (I) (R5
and R6 together constitute a chemical bond) to the corresponding S-alkyl ester (Et and R6 are both hydrogen). This hydrogenation is called catalytic transfer hydrogenation.
enation), ie in the presence of a catalyst and a hydrogen donor. However, it is also possible to use conventional catalytic hydrogenation using gaseous hydrogen.

Catalytic transfer hydrogenation [e.g. C, 13rieget and T, 1. Wegtrick: Catalytic
Tranafar Hydroganation +
Chem, Rev. 75, 567 (1974)], the unsaturated compound is hydrogenated in the presence of a hydrogen donor and a catalyst in a suitable solvent. The excess donor further functions as a solvent.

However, this transfer method can also be carried out in an inert, hydrogen-free gas atmosphere, and is more advantageously carried out under hydrogen pressure, preferably at about 0.1 to 5 MPa.

Catalysts suitable for transfer hydrogenation include palladium or platinum, which may be supported on a suitable support, such as 10% palladium on activated carbon, 10% palladium on lime, or radium on lime.
or 0.1 chino or radium on aluminum oxide; platinum black, platinum and radium halide or oxide (P
bCl2, PtO2), and Raney nickel; complexes of ruthenium, iridium or rhodium, e.g. RuCt
2 (PH5P)! , IrHC42(Mo2SO4'),
IrBr(COXPbsP)3, or RhCt(Ph3
P)s.

Lower alkanols that simultaneously perform the functions of hydrogen donor and solvent, such as methanol, ethanol, n-, or inpropanol, or n-+iso-, 5ee-
Alternatively, it is particularly preferred to use tert-butanol.

Unsaturated compounds of general formula (I) can also be hydrogenated directly. In this case, the relationship between substrate and catalyst is particularly advantageous. Direct hydrogenation is carried out in a pressure vessel from 150°C to
It is carried out at a temperature of 300° C. and a pressure of 0.1 to 10 MPa, preferably 1 to 5 MPa. Suitable solvents are those mentioned above for catalytic transfer hydrogenation, but other protic solvents can also be used, such as glacial acetic acid. The catalyst can be a commonly used hydrogenation agent, such as hydrogen which may be supported on a suitable support such as aluminum oxide, silica dal, activated carbon or zeolite.
Radium, Raney nickel or platinum.

An important condition is that the catalyst is not sensitive to sulfur.

Next, the method of the present invention will be explained in more detail by way of example. However, this does not limit the scope of the invention.

Example 1. Variant a) In a stainless steel autoclave with a working volume of 250 ml, 50 g (0,19 mol) of nocy(n-propyl)-ammonium N,N-di(n-propyl)-
The thiol carbamate was dissolved in 100 m/methanol. After cooling the reactor, the gas phase was filled with acetylene and charged to a pressure of 1.5 MPa. Next, place the autoclave in the 1301? while stirring effectively. : Heated for several hours, cooled and released the pressure. Pour the reaction mixture into 5 volumes of water,
Then, it was extracted with chloroform. The organic phase was dried over anhydrous magnesium sulphate and then evaporated under reduced pressure.

The residue was distilled under reduced pressure to give 23I! (Yield: 61.2%) of S-viny/l/N, N-di(n-propyl)-thiol carbamate was obtained. Boiling point 105℃~112℃/6
mbar.

Example 2. Variant b) The method described in Example 1 was carried out. However, using triethylammonium N,N-diethylthiocarbamate as the starting material, 199 (yield 41'l) of S-vinyl N,
N-17 ethylthiol carpamate was obtained.

Example 3. Variant b) 9.6II (0.3 mol) of sulfur, 821d (0.6 mol) of di(n-propyl)-amine and 100WLl
of methanol was charged into a stainless steel reactor with a working volume of 10001 R1 equipped with a stirrer and an internal heater. The reactor was filled with acetylene and the partial pressure of acetylene and then carbon monoxide was adjusted to 1.72 MPa. After starting stirring, the vessel was heated to 130 °C and kept at the same temperature for 9.5 hours, and then cooled,
And opened it. The reaction mixture was added to 100 d of water and extracted three times with 50 portions of chloroform. - drying the combined organic phases over anhydrous magnesium sulfate and filtering;
Evaporate and distill the residue under reduced pressure to give 26.4g
(yield 47%) of S-vinyl N,N-di(n-propyl)-thiol cargumate was obtained. Boiling point 115℃~1
20℃/12-13 mbar 0 cases 4. Variant b) 9.6N (0,3,9 atoms) of sulfur, 821111 (0
, 6 mol) of di(n-propyl)-amine and 100
d of methanol was charged to the reactor described in Example 3.

The reactor was filled with carbon monocarbide and the pressure of carbon oxide was adjusted to 1.9 MPa. After starting stirring, the reactor was heated and held at 130C for 90 minutes. After cooling and opening, the reactor was filled with acetylene to a pressure of 1.9 MPa and heated to 130° C. for 5.5 hours,
and processed as described in Example 2, yielding 23.91
1 (yield 46%) of S-vinyl N,N-no(n-propyl)-thiol carbamate was obtained. It has the same boiling point as the compound obtained in Example 1.

Example 5. Variant b) 37.311 (1,1711 atoms) of sulfur, 100d (
0.67 mol) of N-ethyl-N-cyclohexylamine and 100 WLl of methanol were charged to the reactor described in Example 3. After filling with acetylene, its pressure was adjusted to 1.4 MPa, and on the other hand - the pressure of carbon oxide was adjusted to 3.7 MPa.
It was adjusted to 2 MPa. The reactor was heated and held at a constant temperature of 100°C for 1 hour, then heated to 120°C and held for 8.5 hours. Analysis by gas-liquid chromatography showed that a conversion of 4° was achieved, giving a yield of 25° of S-vinyl N-ethyl-N-cyclohexyl-thiol carbamate. Boiling point 122℃~124℃/1
2.6 mbar.

Example 6. Catalytic Transfer Hydrogenation 2Ji' (12.5 mmol) of S-vinyl N,N-diethylthiol carbamate was dissolved in 100 d of methanol in a 2501 ffJ stainless steel closed reactor. The reactor was filled with hydrogen and then the pressure was brought to IMPa with hydrogen. The mixture was heated to 50° C. and 5 portions of 0.119 g of 10-thipalladium on activated carbon were added within 4 hours with stirring.

The mixture was stirred for a further 2 hours and then filtered by p.i.
Ta. The F solution was evaporated and the residue was distilled under reduced pressure to give 1.419 (yield 69.1) S-ethyl N.
, N-diethylthiol carbamate was obtained. boiling point 35
~38°C/8 tm Hg.

The same method was carried out using other catalysts and the following results were obtained.

10% platinum on activated carbon 58.3, platinum black 78.6 RhCl3(Ph2P)5 22.1 In the reactor described in Example 6, 211 (10.6 mmol) of S-
Vinyl N,N-di(n-propyl)-thiol carbamate was dissolved in 100 m/m of methanol. After filling with hydrogen, the hydrogen pressure was adjusted to 10 MPa. 50% of the mixture
℃ and 0.1 g of Raney nickel 5 times,
Added within 4 hours. After the addition is complete, the mixture is
Stir for 2 hours, remove the catalyst, evaporate the F solution, and distill the oily residue under reduced pressure to give 1.72. P (yield 85
．． 1) S-ethyl N,N-di(n-propyl)-thiol carbamate was obtained. Boiling point 80-82℃/8■H
g a Example 8. Direct hydrogenation In a 3001 nl pressure vessel, 20 d of S-vinyl N,
N-di(n-propyl)-thiol carbamate 10
0- dissolved in methanol. After adding 1% i on activated carbon + 1 p of radium, the vessel was sealed, hydrogen was passed three times, and hydrogen was added until the pressure was 1.5 MPa. The mixture was hydrogenated at 240°C for 8 hours to give S-ethyl N,N
-di(n-propyl)-thiol carbamate 82%
, while 12% of the starting vinyl compound was recovered.

Compounds shown in the table below were produced in the same manner.

Margin example 9 below. Variant b) 148rd (1,2%) of diallylmine and 57.6
11.8.9 atoms) of sulfur were charged to a 1009 m/vol reactor. The reactor was filled with carbon monoxide to a pressure of 5.9 MPm. After reacting at 100°C for 1 hour,
The reactor was pressurized with acetylene and the hynylation was carried out for an additional 8 hours at 120° C. with several additions of acetylene. S-vinyl N,N-diallylthiol carbamate was obtained with a yield of 10%.

Example 10. Variant C) In a reactor with working volume M30 ON, 257 d (0,18
mol) of dipropylamine and 31.2511 (0,5
2 mol) of carbonyl sulfide was dissolved in 50 d of methanol. The acetylene pressure was adjusted to 1.7 MPa, and the reactor was heated to 130°C to 140°C.
It was held for 0 hours. After cooling and releasing the gas, the crude reaction mixture was distilled under reduced pressure to yield 24.3 g (yield 71% calculated on dipropylamine).

56 g (1,75 g atoms) of sulfur and 154 d (1,2
mol) of di(n-propyl)-amine was charged into a 10100 O capacity reactor. After filling the reactor with acetylene, the pressure of acetylene was adjusted to 1.7 MPaK and that of -carbon oxide to 5.9 MPi. Mixture first
Heated at 00°C for 75 minutes, then at 120°C for 14 hours, during which time acetylene was added several times.

The reaction mixture was heated to 100 QmA! Transfer to a 3-volume flask, add 400 ml of dioxane, and add 17.8 ml of dioxane.
(0.22 mol) of ethyl iodide was added dropwise with stirring. After removing the precipitate, the volatile components of the p liquid are evaporated,
The residue was distilled under reduced pressure. 80℃～98℃/lm
148 g of the main fraction boiling at bar was obtained. Both parts are 20 thi S-ethyl di(n-propyl)-thiol carbamate and 80 thi S-vinyl di(n-propyl).
- composed of thiol carbamate, di(n-propyl)
-The conversion rate of amine was 71% and the yield was 66%-
)Ta.

Less than or equal to ≦, white

Claims (1)

[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 and R^2 independently represent hydrogen, a straight chain, or a branched chain. Branched alkyl group having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, or 1 carbon atom
~6 alkyl radicals or alkenyl radicals having 2 to 6 carbon atoms (these radicals are mono- or poly-substituted with halogen, oxygen, sulfur and/or nitrogen); or R^1 R^2 are together an optionally substituted α,ω-alkylene group having 4 to 6 carbon atoms; R^3 and R^4 are independently hydrogen or a carbon atom number; 1 to 4 alkyl groups (in some cases,
and R^5 and R^6 are both hydrogen; or R^5 and R^
A method for producing a thiol carbamate ester represented by 6 together constitutes a chemical bond, a) General formula (II), ▲Mathematical formula, chemical formula, table, etc.▼(II) (In the formula, R^1 and R^2 have the meanings given above, and Y is a primary, secondary or tertiary ammonium ion, or an alkali metal ion; ), ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) Amine, sulfur, and carbon monoxide represented by (in the formula, R^1 and R^2 have the above meanings); or c) A compound of general formula (III) and carbonyl sulfide; and the following general formula (IV), R^3-C≡C
-R^4 (IV) (wherein R^3 and R^4 have the above-mentioned meanings), and if desired, R^1, R^2, R^3 R^5 and R^ by hydrogenation of the product of general formula (I) in which and R^4 have the abovementioned meaning and R^5 and R^6 together constitute a chemical bond. General formula where all 6 are hydrogen ( I
) A method characterized by producing a compound. 2. Process according to claim 1, in which in process variant a) a thiol carbamate salt solution is used with a concentration higher than 30%. 3. The process according to claim 1, wherein in process variant a) the reaction is carried out in a melt of the thiol carbamate salt. 4. The process according to claim 1, wherein in process variant a) the reaction is carried out at a temperature in the range from 80°C to 200°C. 5. The process according to claim 1, wherein in process variant a) or c) the reaction is carried out at a temperature in the range from 25°C to 200°C. 6. Process according to claim 1, in which in process variant a) or b) an excess of sulfur or carbonyl sulfide is used relative to the amount of amine. 7. The method according to any one of claims 1 to 6, wherein the hydrogenation is carried out by a catalytic transfer method. 8. Claim 1 in which hydrogenation is carried out by a direct catalytic method
6. The method according to any one of Items 6 to 6. 9. The method according to claim 7, wherein an excess amount of the hydrogen donating substance in the transfer hydrogenation method is used as the solvent. 10. The method according to claim 8, wherein the hydrogenation is carried out under a hydrogen pressure of 0.1 to 10 MPa. 11. As a starting material, N,N-di(n-propyl)-
Thiol carbamate salts and acetylene; or di(n-
Any one of claims 1 to 10 using propyl)-amine, sulfur, carbon monoxide and acetylene.
The method described in section. 12. The method according to any one of claims 1 to 10, wherein N,N-diethylthiol carbamate salt and acetylene; or diethylamine, sulfur, carbon monoxide and acetylene are used as starting materials. . 13. The process according to any one of claims 1 to 10, wherein N-ethyl-N-cyclohexylamine, sulfur, carbon monoxide and acetylene are used as starting materials. 14. Process according to any one of claims 1 to 10, in which di(sec-butyl)-amine, sulfur, carbon monoxide and acetylene are used as starting materials. 15. The process according to any one of claims 1 to 10, wherein N-ethyl-N-(n-butyl)-amine, sulfur, carbon monoxide and acetylene are used as starting materials. . 16. Claim 1 using perhydroazepine, sulfur, carbon monoxide and acetylene as starting materials
The method according to any one of Items 1 to 10. 17. Process according to any one of claims 1 to 10, using 3-dimethylaminopropylamine, sulfur, carbon monoxide and acetylene as starting materials. 18. Process according to claim 1, using di(n-propyl)-amine, sulfur, carbon monoxide and 1-propyne as starting materials.