BE631961A - - Google Patents

Description

       

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  Process for preparing organic isocyanates *
There was a series of procedures for the preparation of organic isocyanates from aliphatic or aromatic primary amines and phosgene.

   In these reactions a large amount of hydrochloric acid is produced in each case. This is why it is not possible to prepare isooyanates in which the alkyl or aryl residues contain substituents in this way. which react with hydrochloric acid under the reaction conditions.

 <Desc / Clms Page number 2>

 
 EMI2.1
 are part of these oubat1tuanta among others the group ao - ': tul. the tertiary amine group as well as cyclic lac ;, 4thtra.

   Likewise an adri, a 4'.100y1- or ary1iaooynnat .. whose hydrocarbon r4etoa contain one or more ttnurt groups such as, for example, 3-methc.typropyliooeyanat or) ... (thoxj'l'roryl1l'10Q firlt \ to are so tortiJment attacked, u4a during the piiontdiiatîon that their convent) rc! rarat1on and separation of chloroalooy11Docynnatea obtained as all-product of tloiodon of the ti \ 6: r group are not possible.



  A second possibility of preparation of yeooyanatea ril1- due to the thermal ao1oo1on of phCnxi.quaa of aoidea U-lcoylo: 1rbu.1o.lefJ had o.looyl1eocj'ahnte and phenol and it is used to roll the preparation of lnétl1yl "'i8oo: aLt \ lte et dt l'ttbyl-Isoc.-uniit # 4 This Li4t.âiil $ is however limited to 18ocyanat ..
 EMI2.2
 which are easily volatile and therefore are well
 EMI2.3
 : axa22oa of phenol by distillation. Dso tentatîyoa to rérnrer aune1 of this) 1st. dao 18001 & 00t .. high boiling point resulted in resinification and polymerization of the expected 3uoan :: nto.



  We have just discovered a process for preparing # by thermal cleavage of other alkyl of acid * ii-alkyl- or U-arylth1ocnrbl} .I: 1iquoa, isocyanates orcaniquos with one or more KCO groups in the ne and a. 6auâ, e, which is limited neither by the sensitivity to acids of certain substituent # on the hydrocarbon route of the 1syanate nor by the boiling point of the i, ynates obtained. The reaction is done according to the u1 VlAut given for an itono-iaocyanate
 EMI2.4
 
 EMI2.5
 It remains aliphatic or aromatic which can be substituted auaai by one or more alkoxy routes, cyclic ether, acdt "tertiary alder or other substituents not reacting with.

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 the NCO group.



  R 2 = alkyl residue, preferably an alkyl residue, the raercapto-derivative of which is gaseous at ordinary temperature under reduced pressure.



   The new procedure is based on the fact that at the split
 EMI3.1
 thermal of an alkyl ester of N-s, l, coy acid. or -arylth.o. oarbamic follows as rapid a separation as possible of the isocyanate and alscylmeroapte.n cleavage constituents! before these below the temperature of soiaeion, again reform the alkyl ester of N-alooyl- or Iüwary7.thioaarbamiq acid, us or respectively before a formation of allophanic acid esters or d 'Isocyanurgtes takes place.



  Characteristic of the process is the very short heating of an alkyl ester of 11-alooyl- or N-arylth1ooarbam1que acid under reduced pressure to 100 - 6040, after which the 101 produced from the split are immediately cooled below 80 C and the liquid phase is separated from the gas phase.



   This thermal cleavage with subsequent rapid separation of the constituents is for example achievable by passing the starting constituent in the most finely divided form possible through an enclosure heated to the cleavage temperature and by cooling the obtained cleavage products.
 EMI3.2
 naked in an attached cooler at a temperature of -20 to +5000; thus the isooyanate condenses while the alkaylmer- preferably capturing methylmeroaptan, can be treated as a gas.



   The temperature is preferably between 250 and 400 0 and the reduced pressure is advantageously between
 EMI3.3
 0.1 and 100 mm Kg. The time during which the alkyl of N-alooyl- or N-arylthiooarbamic acid is exposed to this treatment is measured in seconds or in fraction of a second. The reagent is introduced, for example dropwise into a chamber of

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 heated reaction or introduced in a spray form through a nozzle.



   In the case of the drop-drop introduction, the apparatus consists, for example, in accordance with FIG. 1 of a heated container with two nozzles (A '), provided with a bromine bulb and a universal distillation point. The reflux condenser C 'on the distillation bridge is connected to a vacuum pump via a trap F' cooled with liquid air, so the alkyl ester is poured in dropwise. N-alkyl- or N-arylthiocarbamic liquid through the dropping funnel into vessel A 'heated to 100 - 600 * 0 (preferably 250 - 400 0) and we vacuum from 0.1 to 100 mm
Hg.

   Thus the alkyl ester of N-alooyl- or N-arylthiooarbamic acid splits into isooyanate and alkylmeroaptan. The hot gas mixture consisting of isocyanate and alooylmeroaptan is cooled in the reflux condenser C ', advantageously to a temperature of -20 to +50 C. Therefore the iooyanate condenses and goes to the collector B', while that the alooylmeroaptan (preferably methylmeroaptan), which is a reduced pressure slurry gas, is constantly withdrawn by the vacuum pump and is condensed in the trap (F ') cooled with liquid air.



   Particularly advantageous for the process is an apparatus according to Fig. 2 * Here the alkyl ester of N-alkyl- or N-arylthiocarbamic acid is injected as a fine mist by means of a pump. metering (P) through a nozzle (D) in a reaction chamber (A) heated to 100 - 600 0 (preferably 250 - 35000) under a vacuum of 0.1 to 100 mm Hg.



     This creates a very large surface, so that the split is instantaneous. A series of alkyl esters of N-alkyl- or N-arylthiooarbamic acids at room temperature are liquids or low melting point compounds and can be atomized as their melt. We can atomize the

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 EMI5.1
 * wrongly alooylëg of acids X-alkyl- or B-ar, rlthiooarb.-1 which 1 high melting point the state dissolved in inert organic solvents such as trichlorobenebene or para oil * -
 EMI5.2
 end*.
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  The Laotian enclosure (1) contained # au a tube 4'.01 "ollindrîque 70 ma di * tra and 500 ma slow and 11 * and # according to figure 2, internally provided with a" "ft The tube is also divided by several plates (8) porci4e of holes. The heated reaction line follows a y $ fyoi "dienour (X) of my dimension. , which is provided with a cooling tarpon- tin and jacket cooling # and which can be cooled with refrigeration gasket or taus In this place the hot vapors 4'i.oo1anate and dtaloollmeroapian of Preferably methylmeroaptan from the reaction vessel are preferably cooled to a temperature of -20 to 50 ° C. So the isooyanate and condenses and and returns to collector B.

   Alkylmercaptan (preferably methyl # ercaptan) is aspirated by a vacuum pump (Y) through the second cooler for 0 and it can either be condensed in a cooling trap (f) or
 EMI5.4
 well compressed and accumulated in a pressurized tank * binds second cooler (C) prevents small amounts
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 Iscoyanate tees drown in spirit by the morcaptan stream the chosen assembly has a minimum capacity of 100 g 4f1.ayanate
 EMI5.6
 per hour, but you can also pass considerably larger quantities *
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 The isooyanatea thus obtained can optionally be
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 separated by simple distillation all empty, possibly
 EMI5.9
 in a thin film evaporator # of Impurities * at point
 EMI5.10
 boiling high and thus be obtained in a pure form.

   
 EMI5.11
 yields. tn * ieooyanatto pure do not situate> according to the

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 EMI6.1
 nature of the alkyl ester of N-alkyl- or! l-arylth1ooarbatic acid aouala h let scission, between 30 and 60% of the theory * D * will deny very particularly advantageous, the thormic scission 1308 ectara 8 " '0.100y168 of N "alooyltb1ooarbwa1qu acids. can ..- nor be carried out the ur introduction drip tA drop in a heated inert eolvent will send the 18oyannt'D and leu morcap-
 EMI6.2
 tins. The yields thus obtained are in some cases
 EMI6.3
 quantitative rreaque.

   For example one can use oôlvante ouivt.nta s 1-methylnaphthalèno (Péli. 244ebOO) t c11ph'ny1111'ihant (PE 261-262-C), cetyl chloride (1.1, 289 * 0) 0 dîbonzyl-4thr (PE 30000), 1,2-benzopyrene (PS 310-312 * 0), benzyla b4nzoate (Po.Ut> 23-32400) p phenanthrene (P.Se 34000) t dibutyl phthalate (? .Es 340 * 0), gas oils (Peso 300-37000) # technical ter- pheityl (? 4ï * 350 * 0), m-torplienyl (P # B. 360 * 0).
 EMI6.4
 



  In this case, it is preferable to orbit at temperatures
 EMI6.5
 of balloon don aolvanta of 160 h 26000 It is advantageous to use solvents which at these tewp'raturde and soue a pressure of 0.1 to 100 mm Hg boiling only weakly * the 110Ure 3 rolrécente an apparatus for the mine in operation of the crc ± d 5 This apparatus has * composed of the distillation vessel which is fitted with a bromine funnel 2, a therstoatra 3 and a column 4. Column 4 is provided with a column head 5, of a reflux condenser 6 and of a descending condenser 7 as well as of the manifold 8 * the reflux refrigerant 6 are connected by line to a vacuum pump.

   In the distillation vessel 1 and find a solvent which cannot react ateo the ioooyanates and the mercaptans and whose boiling point
 EMI6.6
 must be greater than 20,000. Distillation vessel 1 is heated in aorta that
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 the solvent at vessel temperatures of about 160 to 26040 boils only 1 "alblel: slow at a pressure of eg 0.1

 <Desc / Clms Page number 7>

 
 EMI7.1
 at 100 mm Hg. The alkylated Nalcoylthiooarbamic acid ester to be cleaved by the bromine funnel 2 is then introduced dropwise into the distillation vessel and it thus cleaves into isocyanate and mercaptan. The solvent serves on the one hand as an ideal heat transfer agent for thermal splitting and on the other hand as a diluent.
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  Since the concentration of Ni-alkylthiocarbamic acid S "alkyl ester in the distillation vessel is low by dilution with the solvent, side reactions are largely prevented.



   In column 4 the solvent as well as the fractions not '
 EMI7.3
 further cleaved of N-aleoylthioarbamic acid S-alooyl ester are separated and return to the distillation vessel .- * tion 1. The iooyanate distils through the top of column z, cooled in coolers 6 and 7 and collected in collector 8 in almost pure form.
 EMI7.4
 



  Meroaptan, eg methylmeroaptaa is drawn by the vacuum pump as a gas through the cooled Saur 6 and can then be condensed.
 EMI7.5
 



  The analytically pure isooyanato yields lie between 60 and 99% of theory.



   Suitable for the process, for example, are all N-monosubstituted thiooarbamic acid $ -entera of the formula:
 EMI7.6
 Rl.-N'R.0-SR) n with a lut 2p 5 and plus in which E1 can be an alkyl, aryl, aralkyl <t alooylene, oyoloalooyl residue, which in turn can carry functional groups as per example of dial.aoy3amina, ester, halogen, ether, thioether, acetal, ketal groups. Mention will also be made of heterocyclic residues such as fyryl, pyxiâyle, thiapheyl.e. R2 denotes a methyl, ethyl, propylef isopropyl, butyl, isobut Y the or tert.-butyl residue.



  In particular, mention will be made of the raw materials

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 EMI8.1
 following migrations: S-methyl N-butylthiocarbamate α-methyl N-naphthylthiooarbamate 8-methyl N-phenylthiocarbamate
 EMI8.2
 $ -Methyl N-tolylthiocarbamate
 EMI8.3
 8-methyl N-cyclohexylthiocarbamate
 EMI8.4
 S-methyl N-benzylthiooarbamate
 EMI8.5
 8-methyl N-allylthiocarbamate
 EMI8.6
 8-ethyl N -, .- (2 ethyl.hexoxy) pxopy-thiocarbamate S-methoxypropylthiooarbamate N -, / - di. & Thyxaminoisopantyl- {4, i - thiooaxbam, 8-methyl ate NI-d1ethylamlnopropyl- ('17 -thiooarbamate of $ -methyl 11-e-dimethyl & mînopropyl- (317-thiooarbamate de 0-methyl H-i2,5 8-trioxa-undéoyl- (II) / - thlooarbanate de S-butyl ï f -éthy.meroaptopropyl -. (3,% - $ -methyl th.aaarbamat N '- (3'-methoxyj-butoxyprcpy,.,

  S-propyl X-3-ethoxypropyl7-thiocarbamate S-isopropyl 11-L'-tetrahydroturfuryl-propyl-dther-7-thiooarbamt thi.ooarbamates. of
 EMI8.7
 8-methyl
 EMI8.8
 N-I, 1-diéhoxyethyl- (217-thiooarbamate de 8-methyl N - '"' (2 ', 2'-dimethyl-l', 3'-dioxolanyl- (4 ')) - 2oxapentyl - {,
 EMI8.9
 8-methyl thiocarbamate
 EMI8.10
 S-methyl N-furfuryl..th10oarbamate S-methyl N-octadeoyl-th1ocarbamate $ -methyl X- (Oarbethox, y4thyl) -thooarbamate S-methyl propylene-bee-thooarbamate 0-methyl deao.methylene-14,9-dioxane , 1.2.bie (8-methyl th.ooarbamate), The advantages of the process lie in the fact on the one hand
 EMI8.11
 wide application possibilities are available, because this can also be used to prepare isocyanates with acid-sensitive substituents,

   and because, on the other hand, compared to other processes of thermal scission

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 EMI9.1
 Nique (for example of phenyl esters of 1-.loorlo & ram1- acids) one can obtain an immediate and complete separation of the products of the cleavage, because generally one has to simple-
 EMI9.2
 moves a liquid (1Dooyanate) from a BQ '(xeromptan, for example mtthylmeraaptan).

   Another advantage is that the process can be carried out continuously, thus achieving a high yield of <8% of the starting compounds (8-raters of th1ocarbamic acid N-subet1tut, 8, dicstars of dith101oarbonic acid. ) can be prepared in a simple manner in good yields by reacting primary amines with 8 # 81-dienters of diahiaoarboni acid, bringing into play the reaction partners in such exactly equal amounts. - as slow as possible and eliminating constantly during
 EMI9.3
 reaction to the morcaptan obtained. The removal of the mercaptan is preferably accomplished by applying a vacuum or by entraining it by injecting an inert gas.



   With respect to the state of the art, the fact that, despite the use of equivalent amounts, it is possible to obtain an almost omnipresent reaction can be qualified as absolutely surprising.
 EMI9.4
 complete the amino component with the dieater larequ 'r, i.mi.ne mercaptan formed. It is also surprising that the reaction product is present in this case in a remarkable state of purity and that it no longer needs to be purified, even for the most varied applications. It can be considered practically as analytically pure.
 EMI9.5
 



  In addition, the reaction times are also raoouro11..nt.



  If, in the process according to the invention, one starts from the dithiocarbonate of 8, S'-dimethyl and of butTiaaine, one can account for the reaction by the following diagram
 EMI9.6
 

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 EMI10.1
 As the S, S-dialkylated dithioaarbonic acid estera are also considered as oxyl, but preferably the esters are used.



  0100y1u lower, in particular methylene and dthyliquet The ceroaptan obtained in the r'-JoUQl1 can all the better be <lit-.in that a boiling point is more band, As anines it is envisaged for the colon process the invention. tion of the primary amines uliphatic, cyolbaliphatic uliphatiquco inouturéto as well as the hôttrocyo11qu .. and dln: 1I1ne. oorroarJondnn t.OG. Loua aaiMes can present outside created the carbon structure of only substituents! such as 4ca i-roupeu alkoxy # acetal, th1o {ther and tertiary amine.

   The various paragraphs which can be used do indeed present a different reactivity. They are practically not
 EMI10.2
 limited in principle in their use by the constitution of the carbonaceous atruotide *
 EMI10.3
 As examples of aainea used. preferably one will mention in particular s butylanine, #ethoxypropylaaine, ethoxypropylaaine, 3- (2-ithyl) -haxoxypropylamîne, 1 {, et-diamino. dipropyl-6ther, butane-1,4-diol (t ') -diero1nodiprOP11-eth.r, proplMl1ne f e, .1no (; thylaotal, -thylmsraaptoprapylaz3ne, eina-dria de, p4lythera as well as oyclohexylam1ne.
 EMI10.4
 



  The reaction is carried out at temperatures between -10 and
 EMI10.5
 -t-150 ° C, preferably between 0 and ± 3C.



  For the reaction, 8vnta &, u..ment the amine admit to orient it in such quantities that for 1 mole of dieeter there is as well as possible one mole of amin 4 rrima1r .. The mixture is then heated to temperature. for better mixing it is advantageous to stir or
 EMI10.6
 shake. Removal of the mercaptan obtained during the reaction
 EMI10.7
 can be done in a number of ways.

   It has been found to be particularly advantageous to carry out the reaction in a vacuum.

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 EMI11.1
 Ideally at pressures between 0.01 and 600 ram Hg. $ # ruc oa, p tan can however also be expelled by passing an inert gas such as nitrogen through the reaction mixture. After completion of the reaction the product of reaction in pure form.

   Treatment is generally not necessary *
The process has a number of advantages: It is carried out under simple reaction conditions and without the use of auxiliary substances, and it provides pure reaction products in high yields.
 EMI11.2
 



  The thiooarbon1 acid d3.aaters can be prepared only by reacting the solution of a meroaptan and an alkaline 4hydro- xyda in water with a solution of phongene in an inert solvent immeasurable in water. , with mid long intense phases and at temperatures below 30 * 0. ta riao "tion can also be performed continuously.



  It can be described as absolutely surprising that the
 EMI11.3
 phosgene hardly reacts with water and alkali hydroxide, but exclusively with mercaptan. This is really
 EMI11.4
 surprising because the known processes operate in absolutely anhydrous biliez. It is also astonishing that, with a slight two-phase mixture, for example in a column with bodies stacked according to the principle of the counter-current one obtains not the d3.aater of acid dthacarbanà.qua conforming to the invention, but the corresponding monoester. To get the
 EMI11.5
 diester according to the invention, it is therefore absolutely necessary in the use of two liquid phases to obtain an excellent mixture of the phases.



   When the process according to the invention starts with phosgene and methyl mercaptan, the course of the reaction is shown by the following diagram
 EMI11.6
 

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 EMI12.1
 These materials can be used: aleoylsEercaptans, cycloalcoylmercaptans as well as arylmercaptans. The hydrocarbon residue of these morcaptans may further be substituted by alkyl, aryl, alooxy, aroxy, thioether, ester, nitrile and nitro groups. Likewise, halogenated derivatives are
 EMI12.2
 employable. The mercaptans to be used are therefore in no way limited with regard to their constitution.

   Preferably, alkyl mercaptans with alkyl residues having up to 20 carbon atoms are used as well as arylmercaptans which contain a phenyl or naphyla residue.



  As meroaptana which reacts particularly well, we will especially mention methylaercaptan, ethylmeroaptant isopropylmeroaptan, butylmer-caftan, dodecylmoroaptan, methoxyethylmeroaptant phenoxyethyl-aeroaptan, as well as tniophenol, halothiopheno18 and alooxythiophenola.
 EMI12.3
 Solvents are used as solvents which are not poor in water and which do not react with phosgene or with alkali hydroxide * To this category belong in particular.
 EMI12.4
 aliphatic, aromatic and oyo10a11- phatic hydrocarbons as well as their ohlorination products, for example therefore benzene, toluene, xylene, ohlorobenzene, oyoloheyane, gasoline and lierolne,

   
Among the alkaline hydroxides, use is preferably made of potassium hydroxide, sodium hydroxide and, however, also lithium hydroxide.



   As other auxiliary substances can also be added in the course of the reaction emulsifiers to facilitate the formation of a free suspension. In general, however, the use of emulsifiers is not essential.



   The reaction is carried out at temperatures below

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 EMI13.1
 3000 # preferably between 0 and 20 * 0.



  To carry out the reaction, 2 to 3t, preferably 2.0 to 2.2 moles of eroaptan per mole of pho8shno are used. The alkali hydroxide is used in an equimolecular amount relative to the mercaptan. To the reaction, the aqueous solution of meroaptan and alkali hydroxide and the solution of phosgene in the organic solvent are added together and the phases are mixed thoroughly as well as possible, for example by stirring or shaking vigorously.



  The content of aqueous solutions of alkali hydroxide is chosen preferably between 2 and 5 moles per liter of tolerance. It has also been found favorable that after the end of the reaction the pH value is still weakly alkaline * $ before
 EMI13.2
 tageuaem, have between 7.5 and 9.



     The necessary phosgene is advantageously added to the solvent directly before the addition to the reaction vessel.



  It is then particularly advantageous to pass the
 EMI13.3
 solvent through a re! ro1d1Boeur and add the phooeene to the cooler. In the cooled solution the phosgene dissolves particularly quickly. Depending on the nature of the solvent, the most favorable temperature during the addition differs somewhat. It is generally between +5 and
 EMI13.4
 -t-10'C.



  In the same way, the morcaptans can also be dissolved, in the case of eaeous mercaptans, in the aqueous alkali solution directly before addition to the reaction mixture.



   The treatment of the reaction mixture is carried out in the usual manner. The organic phase is separated and the diester is recovered by distillation.



   In a particularly advantageous embodiment, the reaction according to the invention is carried out continuously.

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 Ch 1'lh "dei roundly octracu-'hmf '. L'nrtioul1r.". Nt
 EMI14.2
 6 coiled.
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  In figure 4 shows an apparatus for the execution of the lei renction, the! (\ 1t in the reaction tower 1 # la- q118 have provided itnpitatour several fins 2.



  Lntrc when xon * 8 of imitation had found dune the tower of reduction in zones of 1 "121'08 z travore l08 (lUelleB the phoegt.ne die- under dauo the organic nolvart have poop4 in going up * To carry out the re #iotiot., we dress from the illioogenic cylinder 3 If phoor.l..no by the pipe 4 dt ,, naked the cooled
 EMI14.4
 SWEET '5. It is cooled by the cooling jacket 20
 EMI14.5
 b a temperature bnene anrop "t, o. Sit1ul tOllr: umt one adds to 1 '<1rt..1r of the vtockuco tank 6 tuff read jonpe 7 of the solvent dnno the cooler. In this place the plioogen dissolves dai.u the solvent * The obtained is fed by the conduct ii read the reaction tower and it enters a little at the bottom end 9. The organic phaoe rises slowly in the tower and it out strongly (, 18r.céo far l agitator with the jqesa phase.



  Read the solution of the in the aqueous solution of alkali hydroxide out Introduced 4 from the storage tank 10 by means of the pospo 11 d18 the upper part of the reaction tower in 12. The aqueous solution is then left largely in the tank. turn from top to bottom where it is very strongly with the ort phase, mnime. Either this continuous realization of the reaction it is advantageous to employ the olvanta which has a specific gravity less than 1.1.

   In this coo the principle of the counter-current in the reaction tower is exouted in corte adding the organic solution at the bottom and the
 EMI14.6
 aqueous solution on top.
 EMI14.7
 By the conduct of ah..fee 13 the aqueous solution of
 EMI14.8
 sodium chloride is subtracted from the tower and sent to the

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 EMI15.1
 means of the pump 14 in the tank 15. the solution of the 8 S Kii * 8ttr of aoidt d1thioaarbcn1qut in the organic solvent is withdrawn at the head of the reaction tower in 16 and flowed into the tank of st9o! t & g < 17. Line 18 constitutes an inspection window for recognizing the boundary surface of the phases.



   The reaction tower is cooled with the aid of the cooler 19 to the desired temperature. The heat of reaction in this embodiment continues to be more simply dissipated than in the batch process.
The method according to the invention has a series of advantages. It starts from simple raw materials, does not use
 EMI15.2
 that simple auxiliary substances is effected under simple reaction conditions and results in high yields.

   In addition, the continuous reaction is particularly simple to carry out Example 1
The flask A 'according to Figure 1 is heated to 330 C by a metal bath and the upper end of the condenser to
 EMI15.3
 reflux 0 is connected, by ± 'via a trap F' cooled with liquid air, to a vacuum pump and the flask is placed under a vacuum of 15 to 20 mm Hg. then introduced dropwise.
 EMI15.4
 over 2 1/2 hours 109 g of S-methyl 3-ftetrahydsofur "* turyl-propyl ether-1-thiooarbamate" through the dropping funnel into the heated flask. The substance splits into 3 '" tetrahydrofurfuryl-propylether <-l -'- isocyanate
 EMI15.5
 
 EMI15.6
 and methylmeroaptan. the isocyanate is condensed through the reflux condenser and flowed into the header.

   73 g of 3'trahydrourfuryl-propy.ét2er.-izaawnnta are obtained again

 <Desc / Clms Page number 16>

 
 EMI16.1
 impure, from which, by distillation we emptied 112 * 135 * 0/15 ma Ug, 34 g of Ieocyanate are obtained in the analytically pure form in the form of a colorless liquid * This corresponds to a yield of 40 % of theory. Methylmeroaptan is
 EMI16.2
 sucked by the vacuum pump through the reflux condenser and condensed in the cooling trap.



    Example 2.
 EMI16.3
 



  A steel tube 70 nun in diameter and 500 ma long fitted with a Bosch nozzle and raised to 30,000 by a heating coil with a coil refrigerant of the same dimensions cooled by brine to a temperature of -20 to .0 f7 with connection to a manifold, with a second refrigerant, a liquid air cooling trap and a vacuum pump (according to figure 2), is placed under a vacuum of 8 to 10 mm Hg.



  446 g of N-3- are then injected over the space of 3 to 4 hours.
 EMI16.4
 (2¯fcthyl-hezoxy) 8-methylpropylthiooarbamate with a Boech metering pump through the Bosch nozzle and the vacuum is maintained at 8 - 10 mm Hg. In the collector, 361 g are collected.
 EMI16.5
 of 3- (2¯ethyl-hexoxy) -propyl- <isooyanate still impure
 EMI16.6
 and, in the liquid air-cooled cooling trap, 50 g of methyl mercaptan. By vacuum distillation we can
 EMI16.7
 Obtain from the crude isooyanate at 100 - 103 0/0 "mm Hg 170 g of the analytically pure compound, The residue of the distillate.

   tion is still subjected under the same conditions to a thermal scission and it gives after the distillation another 90 g of
 EMI16.8
 3¯ (2¯t5thyl¯hexoxy) -propyl¯iaocyanate. In all, therefore, 260 g of pure 3w (26thyhexaxy) -propyliaaoyanats are obtained in the form of a colorless liquid. This corresponds to a yield of 72% of theory

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 EMI17.1
 As in example 1 we noinde th.1quemont. 370 * 0 we 2 mm do 32 g of deo6a4thyltmē4 9-dioxe * l | 12¯dithiocarbaraatt of 5-methyl and we thus obtain 11 g of cUoameth, yl61o-4.9 .. di.oxa-1> 12 * dlisooyanate.



  OC-tt ... OR2 ... CH2-CH2..0-CH2-OH2-QR2-0H2-0-0H2-CH2-ou2-uao By vacuum distillation 141-144 * 0/2 mm Hg can be obtained 702 g of compog in analytically pure form. the state of a colorless liquid. This corresponds to a yield of 3le of the
 EMI17.2
 theory.
 EMI17.3
 



  Exlet Commo & Example 1 we introduced the liquid form 280 g of! .3-pheny16thyl-thiooAtbaroat. of $ -methyl (P. ?. 55-5740) under reduced pressure (70 on Hg) by means of a dropping funnel # enautrie 4 the water vapor, into the decomposition flask heated to 55O-34O ° C. In the collector we collect 220 Il 4'lsocyennte not yet completely pure, from which we obtain by intîllatîon we empty to 104-106 * 0/15 my lig 147 of /.3"phenyl thy11eooyenate pure in the form of colorless liquid, which corresponds to a yield of 70% of theory.
 EMI17.4
 Example
 EMI17.5
 300 g of '- ("-' thoxy) -butoxy-proP11-l-th10oarbntc of 8-ethylb conae in Example 2 are sprayed and it is removed therj.quo'aont to '00 0/8 mm Ha.

   After twice repeated noinuion and vacuum distillation 170 g of 3- (3Hne'thoxy) - butoxy-proryl-130cyant are obtained. t Cl1, ... OH "C1I2 ... CH2-0-CH2-CH2-CH2-NCO CH3 as a colorless liquid boiling at 115-117 * 0/15 aa Hg in the pure state, This corresponds to a 71% yield of 1 <. theo-
 EMI17.6
 laughs.

 <Desc / Clms Page number 18>

 
 EMI18.1
 



  1 ... 1t't 6.



  We add:; other 1 drop 25 6 do N-bu1; yl ... t11ooarbamat .. de -., Gti ;; to Az the molten state (ï.ï. 35 * 0) as in example 1 in >: i? c; l. ::: r: of decoration ('h! \ lft4 Ù 250 "270 * 0 eOU8 a vacuum, i1 .0 na Lis. Apr! -8 ocissicn rlr6téf' ot subsequent distillation in 0 0t h: nt 5.1 [; 4o rz-F: uty3-iacyar.ta, PE 45-50 * 0/60 ma Hg * Ciiel ocrroc. "on 1 h a yield of 30; c of theory.



  :; ";: '1: 1c 7.



  CE, w;:., A. ltexo! .. p1 rice on ec111de thort1iquemen't 40 g 4. H-3-: tlzocy-rotTyl-tllioatelbn ^: aac Je 8 nthy.o '' 400C / 20 aa Hg.



  When this is stopped, 12 $ of 3-t'tboxy-propyl-iaooyanat is obtained in the form of a colorless boiling liquid which is 1I1F Hg.



  This cofr <! 6uond a return of 41? ' of theory. r '(' '; 1' 11 ", -l, - DIJ lb decorlte at exel '\ I.1e 2 100 g of 1-diuthyl \ ninoinor9ntyl- (4)" thiccarbcate de 8-athyi * rented empty (7 r lie !,) and or. e1HotU $ the thermal soisaion Il 350 * 0. tt '.! t given that read IJCir: .11on avoe a single paooace is not \ 1nC0r co'iplitô on' \ 111 : 1 (121 ttl the renotion product 1Io0j "ana: U obtained twice more by the eco" '11oo1 tion apparatus. We c: i. # Ïcza cinai 55 #; de l-diethylaainoioo? Enty3- (4) -ieocyanate u1 is not yet coa: .ltaw, and rur. By distillation under Y1ùI1 one obtains, t 20. ccupoaé boiling at lOdoC / 10 aa Hg zou In 4àoi-ne 1tÙyU1u.:; T :! nt pure, which corresponds to a yield of 2: 5 fi 'of Ifs theory.
 EMI18.2
 
 EMI18.3
 



  1.:xc'.I)(lo.



  CoKe 11 the oxasple 1 we split ther # iquecent to 360 * 0 we have a vacuum of 18 cs: 3 Hg. 50 g of ... d icu! ThylaminoproPl1 -, - t} .t100Ar.ba- mate of S- = .ethyl. tar distillation of the final product

 <Desc / Clms Page number 19>

 
 EMI19.1
 crude under vacuum, 4> 5 g of pure 1-dimethylaminopropyl * lr3- "isocyanate are obtained, boiled at 8000 under 31 mm Hg. The amount amounts to 20.5% of the volume.
 EMI19.2
 
 EMI19.3
 F:, xempt, e * 9.



  In accordance with Example 1, 35 g of 8-methyl 1-methoxypropyl, 3-thipoarbamate are slowly introduced dropwise at 300 ° C. into the decomposition apparatus under a vacuum of 190-200 mm Hg. After repeated cleavage. several liver and subsequent vacuum distillation gives a total of 17 g
 EMI19.4
 pure methoxypropylT'3''isocyanate, boiling at 102 * 0/186 mm HC, which corresponds to an overall yield of 65% of theory.



  OHO-CHCHCHN. = C = 0 Example 11.



     We introduce slowly drop by drop and split thermie
 EMI19.5
 only 125 g of 2,5,8-trioxa-undéoy11thiooarbamate of S methyl at 360 0 under 13 mm Hg in accordance with example lo Under these conditions 88 g of crude cleavage product are obtained from which can be obtained, by distillation fractional
 EMI19.6
 4140-141 0/14 mm Hg, 67 g of pure? 15 # 8-trimoxa-unddoYl-11-isOCyanate. This corresponds to a 66% yield of the theory OH-O- (CHOHp-0) -CHCHg-CHg-N'.C-0 ffxpmple: i * L2.



  In the decomposition apparatus described in Example 2, 87 g of 25t6,11-tetra-oxa'-ttradéoyll4'-thiocarbamate de $ -methyl at 350 C under vacuum (7-8 mm Hg) are thermally separated by
 EMI19.7
 double atomization. The fractional distillation which then takes place gives, starting from 78 g of crude product, 37 g of

 <Desc / Clms Page number 20>

 
 EMI20.1
 ,,, x.ttrawoxy -ttre, dcy .-. 4. pure ocyanate.



  We thus calculate a yield of 503 of theory c. (CHciw -0) a-.c2..Ct2.rr.c0 lI.e: ': I> 0 12.



  In accordance with the example, 42 g of S-methyl 1-ethylmeroaptopropyl-3-thiocarbamate (15 mm Bzz. Le) are slowly introduced dropwise at 35000 μ into the alcohol apparatus described. raw color product obtained
 EMI20.2
 slightly brownish gives after fractional diatillation 12.5 g
 EMI20.3
 of pure thy.rasrcaptoprogyl-.3.eooysasate as a boiling colorless liquid .i.2 ... 4 C'9 mm Hg. This corresponds to a theoretical yield of 39.5 i.



  Ci-S-Ci-CIi-CH - it4C = p 3JXeily According to Example 1, 55 g of 8-methyl 1,1-didthoxyo'thyl-2-.thiocarbaraate are split at a temperature of 340 ° C. and under a vacuum from 12 to 15 mu H. From the raw i'ieooyrnata obtained
 EMI20.4
 can be isolated by fractional vacuum distillation 17 g of
 EMI20.5
 Pure 1, .- diethoxyEthyl-2-ieocyanate having a boiling point
 EMI20.6
 of 83 * 0/30 mm Hg. From this the calculated yield is.
 EMI20.7
 40% of theory.
 EMI20.8
 
 EMI20.9
 x3t ". i.8e
 EMI20.10
 Rubber in Example 2, injected and thermally split
 EMI20.11
 in two darning 200 g of 1- (2 ', 2l * diraethyl * 11 3f diox0lanyl- <(4')) - 2-oxapentyl-5-'thiooarbaïuate from wat3iy. â 350 * 0 creates a vacuum of 5 to 7 rara Hg in the decomposition tube.

   By fractional distillation in a subsequent vacuum of the crude ionoyanate produced, 68 g of 1. (2.2 '. D3: thy.p1', 'd.vcoly,

 <Desc / Clms Page number 21>

 
 EMI21.1
 (5 ')) - Pure 2-oxap9ntyX-5-leocyanat9 boiling at 130-132 * 0/10 mm Hg. The residue is further split under the same conditions and gives an additional 19 g of pure ooapoaé. In all we get
 EMI21.2
 67 g colorless dliaoayanate. This corresponds to a yield of 49.5% of theory.
 EMI21.3
 



  Example16.
 EMI21.4
 



  C28C-CH2.CR2-H2-HC = 0 In a balloon due 250 cm? with three tubing provided with a bromine funnel, a thermometer, a 30 Vigreux level column have a column head, a reflux condenser, a descending condenser and a collector according to figure 3. 100 g of benzyl benzoate are added and
 EMI21.5
 heat the bath to 2fl 'C. The temperature of the flask of the benzyl benzoate must be between 195 and 19600 at a pressure of 35 to 40 mm Re.

   Then b84 g (m 5 moles) of N -, - ethoxlpropyl-th10oarbamat are added dropwise over the space of 11 hours. of pure 8-methyl (PE 10000 / 0.6 mm Zigs in the three-necked flask * The '-'thoxpropyl-1sooyanato almost rur thus distils at a boiling point of 75¯CO O under 40 uua Hg 3 l' colorless liquid state and it is collected in the manifold, the methyl mercaptan is condensed in a cooling trap.



  Yield: 640 g (or 99% of theory).
 EMI21.6
 



  Analysis s hold. 32 t St of liCOt found 29.05 of NOO The product can be further purified by distillation,
 EMI21.7
 P.E. 53.5-54OC / 12 mm Hg.



    Yield: 574 g (89% of theory) Analysis: C6H11NO2 (129.2)
 EMI21.8
 hold. 32.5 SOO, found 30.6% NCO.

 <Desc / Clms Page number 22>

 
 EMI22.1
 Lye; @le, 17.
 EMI22.2
 
 EMI22.3
 



  COi: '.:' 10 in Example 16 hot acindo 510 g (2.7 aolee) le l .-} - isopropoK.) 'Proryl-thlocc # ba,: Jtite de 8-né "thyle Pl 105 - 110ClCjOtZ uns related, The tor.iper6.ture of Win is 235 "C, the temperature of 1; enÍo [tù do 111311 ..:; .. '10 dunne the ball must be between 201 and 205 * C and lu precaion between 25 and 30 years lig.

   The 3-ioopro- pôypr0t.yl <.isocy <mat <'distillation h 75- * HO'C / 25- * 30 at Hg forms colorless liquida and can be further purified by distillation 1 3 cock, 5 g (drink 78. of the theory}} PE 72 * 0/15 mee-li diasz;, rtu 1 C-1! 13}; Z (143,2) C7cu:: J 29,5) 'de:. " C0f found 28.05 of .Ib * 00 1- ..,;: 1 ', 1! 2lïm râ; .x .t iif "",: "i ^'", '1 "ï" "rs1 iir: Y CH; le lu; lH1. \ re dl. <.: 1'1te to o: l: e: 1rlc lô for 3 ëthoxyprô¯; y'i-isoctruzute, we include therniquesient 67th g (* 33 aïolea) of; "'- :; vc ... butoxy}, rorj'l th1ocQrbtt: ate do 8-aC'thyle pure (' .i :. 133 * 0 / 2,5 r.:nl d.



  The <t: .. ± sr, ture of the bath must u1 amount to 2i $ 0 * Cf the temp'ra- turv J'.J. cc content: zax 1215-'220 "C and the test at 45 mm Hg.
 EMI22.4
 
 EMI22.5
 



  The crude product is distilled to a boiling point of: 3-55 C / 45 rr He forms a colorless liquid and is then purified by distillation.



  Yield! 449 C (or C5 ± of theory); 2.?.* 72.5 0 (11 cm Hg) Analysis 1 C & H1502 (157.2) Wedge. aC, 75? ' of !! C0, found, e6.5: of ± C4.

 <Desc / Clms Page number 23>

 
 EMI23.1
 ffxqtala ..



  ZXOMU> 12 i2b
 EMI23.2
 
 EMI23.3
 Impure 1044 g (m 4 moles) of N '* 3' * (2 ** ethyl) <- hexQxypï'opylthiooarbamate 8-mdtliyle in the apparatus described in Example 16. As solvent is used 100 g. dibutyl phthalate. During the thermal split the bath temperature is 235 C the temperature of the dibutylo phthalate in the flask is between 218 and 222 * 0 and
 EMI23.4
 the pressure is 13 nrn Hg. The 3 '* (2' - 'thyl) -' hoxoxyproryl-i <ocy-anato distils with a boiling point of 130-13500 / 13 mm Hg as a colorless liquid.



    Yield! t 704 g (or 83% of theory)
 EMI23.5
 The crude product can be purified by distillation (P..E. 6e1 9e5 rm Hg). Yield: 606 g (or 71% of theory).



  Analysis! 1 12H23NO2 (213.3).



  Hold. 19.7 of NCO, found 18.6 of NCO Example 20. '
 EMI23.6
 
 EMI23.7
 As in Example 19, 160 g (no @ 686 mole) of unpurified S-methyl α6xtaydrouxurypxopyxdherthaaax "ba mate are thormically split. The bath temperature should be
 EMI23.8
 during the emission rise to 240 0, the temperature of the dibutylt phtamate in the flask between 218 and 2eOOC and the pressure at 20 mm Hg. The '-t6trahydrofurfuryl-propy16therMli80CYanate distills with a boiling point of 11Q ma Hg as a colorless liquid (round: 120 g) and can be purified by distillation (PE 149-150 * 0/20 mm Hg).



  Yield t 76 g (60% of theory)
 EMI23.9
 Analysis! s CHH (15.2 Calo. 22.65 NOOT found 22.0 NCO.

 <Desc / Clms Page number 24>

 
 EMI24.1
 



  3Een; p 21.



  As described in Example 16, we split thermiquetawat in a 1000 om3 three-nozzle flask 771 g of N "3'-nethoxy- '
 EMI24.2
 $ -methyl propylthiocarbamate (crude product) by introduo-
 EMI24.3
 tion dropwise in 400 e of benzyl benzoate at 05-22500 Doua empty (12 mat Hg). This gives 501% of '-m6thoxypl'opyl-isocyanate having a boiling point) 6.5-8.0/12 mm Hg, which corresponds to a yield of 92 of theory (relative to the thiocl1rbo ester.:niq\4e iiapur).



  Analysis t C5H9021; (115ek) i wedge .. '6.5; of 1100t found 36,) 8} of 1IC0.
 EMI24.4
 



  Example 22.
 EMI24.5
 



  C2H5-S-CH2-CH2-N = C0 In accordance with Example 16, 1143 g of non-8-methyl N-2-ethylmercaptoethyl-thiooarbamate are thormically split.
 EMI24.6
 purified by slow introduction Drop by drop into 400 g of benzyl benzoate at 210 0 under vacuum (12 mm Hg). A 67-69 "0
 EMI24.7
 under 12 mm kg distill 635 g of crude isocyanate (75% of theory). By distillation, 475 g of pure 2-ethylmaroapto-4yl-inocyanate boiling at 72-7390 soue 12 mm Hg are obtained. Analysis t CSH90TIS (131.20) 10alo. 32tO e of NOO; found 31 65Î of N00.
 EMI24.8
 



  Example: 2%
 EMI24.9
 
 EMI24.10
 We remove heat from 225 S (0.92 mol) of N '- (2-methyl # oyclohexoxypropyl-thlocarbamat of 0-methyl (crude product) oomma in Example 19.



  The bath temperature must be 250009 the temperature

 <Desc / Clms Page number 25>

 
 EMI25.1
 in the flask of ± 30-240 * 0 and the pressure of 40 ma Ho * The t - (2.mthyl-vyalahaxd9typropyl-ioaywnate dittille at 155 - 16tCfO mm in the form of a colorless liquid (yield 169 8) and it is purified by distillation and empty us using a column (PE 137 * 0/15 mm Hue). Yield s 110 g (ie 61 of theory) Analysis CllH1gU02 (197.3) t oalo. 21.3% of NCO, found gO, 2? S of .00.



  Exempl. 0 4Hg-lm-C-S-OH, A 30.5 (0.25 isolates) of 41th1ooarbonat. of Sf8f-dimrfthyle is added slowly; drip to penis while stirring all empty (75 mm Hg) l8e3 g of butylamina. Then stirred asleep at room temperature for 5 hours * Mthylmaroaptan
 EMI25.2
 obtained in the course of the reaction constantly distils a vacuum
 EMI25.3
 you start from the reaction mixture and it is captured in a collec-
 EMI25.4
 strongly refrigerated.

   As residue one obtains in
 EMI25.5
 reaction vessel 34.5 g of B-butylth1ocorbamat. of 8-aethyl (theoretically a 94 compared to butylamine) melting at 4.0. om le, 2 ,,
 EMI25.6
 In a 2-liter flask, three tubes are added
 EMI25.7
 dropwise to 610 g (a 5 aolea) of 6, S'-dimethyl dithlooarbonate while stirring at 10-15,0935 g (- 5 moles) of 3-2-.éthy7.hexaxy-propylara9.ne. We then apply a vacuum of envi
 EMI25.8
 ron 100 mm Hg and stirred for 3 to 4 days at the temperature
 EMI25.9
 ordinary.

   The methylmercaptan obtained in the reaction is eor-
 EMI25.10
 pulled and condensed in a cooling trap *
 EMI25.11
 1290 g of pure 3-methyl N-3 "(2-cthylhexoxy) - propyl-thiooarbamate of formula 1 remained in the flask.
 EMI25.12
 

 <Desc / Clms Page number 26>

 
 EMI26.1
 (JvUI / Torso of a Colorless liquid. This oorreuns o a rendering ...



  I ... t. of I) -the theory. The thiocal'bam1Ilu ester, diûoapôa to lu diot111ot1on.



  Ar1, .lyuo s nUl rlO25 (261, 4) calo. N 5i36 8 12.2? found N5.4 5 11.75
 EMI26.2
 ia 1 fJ: u 2 tu Gli3-0-CFi QÜ2-CFI2aïli - CB.II
 EMI26.3
 For example 25, 61 g (m 0.5 mole) of the ditliîocnrbonnte of 8tSt-d11tthyle are made retire with 51.5 a (tu 0.5 mole) of 3- * thoxyrroFyiEînine * We obtain b4.5 g of K¯3 ethoxypropyl thlocnr '* Tvte of 6-t-Etfyle under tome of colorless liquid (w Çb;' of the theory). The 8ubetf'.no9 this already analytically pure. At distillation it does not deoompooe.



  Miulyse 1 C7H15t: 025 (17té3) calcula t C 47.42 H et53 0 18.06 li 7t9O 6 1809 found t C 47tû9 Il 8.58 0 18.36 K 7.93 S 16.7 It except 2 on made rea:! ir 244 g (# 2 mole.) of u'4t .-, ioc, rbor, u + u of S.S'-d1r.étr.ylo with 204 g (1 mole) of l, 12-diano- 4.9-'dloxa-'dod <! C {tne.



  346 g of dcalethylbne-4,9-dioxa-l, 12-b18 ... 5 - ethyl thiocarbumate of formula are obtained.
 EMI26.4
 
 EMI26.5
 under force of colorless crystals * This corresponds to a round
 EMI26.6
 Ment of 99 of 3L & theory, The compound can be re-installed from t1thano by cooling b. -4040. This gives 29b e de aubetance rure ayunt a melting point of 71.5 - 72.50C.



  Analysis C14 l128 li 2o4s2 (352.3)

 <Desc / Clms Page number 27>

 
 EMI27.1
 hold. 0 47.72 H 8.00 N 7.94 8 18.19 Found C 47.16 H 8.25 N 7.79 S 15.9.



  Example 28.
 EMI27.2
 



  As described in Example 2 for $ -methyl N-3-C-ethylhexqxz7r propyl-thiocarbamate, 61 g (- Os mole) of dimethyl dithiooarbonate are reacted with 79.7 g (m 0, 5 mole) of 3-tetrahydrofurfuryl-1-amino-propyl ether and 117 g of N- (3 "tetrahydrofurfurylpropylether-fl) -thiocar * bamate of the formula are obtained.
 EMI27.3
 in the state of colorless liquid under a pure foras (which tightens
 EMI27.4
 pond at a return of $ 100 of theory). Compound 00 is composed by distillation.



  Analysis: CIOIÎ19NO 3S (233t3) calculated 9 C 51.48 H 8.21 0 20.57 N 6POO 0 13.74 Found: C 51.67 E 8.20 0 20.61 N 5.98 8 14.2 Example 2 9
As in Example 25, 122 g (* 1 mole
 EMI27.5
 of 8,81-dimethyl dithiooarbonate avoo 161 g (m 1 mol) of 1-amino-4t8-dioxa-7-methylnonane and 230 g of lN-nonyl-4,8-dioxa-7-methYlthiooarbat are obtained. of pure S-zethyl of the formula
 EMI27.6
 in the state of a colorless liquid (which corresponds to a theoretical yield of 98). In the distillation test the substance decomposes.
 EMI27.7
 



  Analysis 1 ale21 -03 3 (235.4): calculated N5.95 S 13.62 found N 6.1 S 12.3.

 <Desc / Clms Page number 28>

 



    Example 30.
 EMI28.1
 



  198 g (m 0.8 mole) of 1â-thia-pezztadéaylatn.ns are slowly introduced dropwise from a dropping funnel heated with hot water into 98 g (0.8 mole) of S dithiocarbonate. , S'-d.méthy.e 20 0, which is in a stirring and vacuum apparatus similar to that of Example 25. After 8 hours of stirring, the contents of the flask solidify.



  In order to be able to complete the reaction, the mixture is stirred at 40 ° C. for a further 10 hours. The methylmercaptan that is released can
 EMI28.2
 to be condensed in a strongly cooled trap. After recrystallization of the crude product from toluene, 199 g (= 78% of theory) of S-methyl N-13-thia-pentadecyl-thiooarbamate of formula
 EMI28.3
 CH 3- (OH2) 11-s-cii 2-OH2-lai-cōsaH3 mp 53-57 "0.



  Analysis s C16H, 30ns2 (319.58) calculated C 60.14 H 10.41 N 4.38 S 20.07 found 0 60.32 H 10.35 N 4.20 S 19.70 Example 3 \
 EMI28.4
 A 183.3 g (m 1.5 moles) of 8, S. wdime dithiocarbonate. Thyl is slowly added dropwise under vacuum (65-15 mm Hz) and with stirring 407.2 g (<e 1.5 moles) of 15oxa-ootadeoyl amine and the methylmercaptan which is released is collected in a strongly cooled room. The initial foaming of the reaction mixture is combated by reducing the vacuum. After 10 hours of stirring at room temperature, part of the reaction product precipitates.

   The mixture is stirred at 40 ° C. for a further 12 hours under vacuum and the mixture is then dissolved at this temperature in the smallest possible amount of toluene. After removing a little (35 g) of difficult soluble product with suction, the filtrate is cooled considerably (-50 ° C.). The
 EMI28.5
 Analytically S-methyl N-15-oxa-octadecylthiocarbazuate

 <Desc / Clms Page number 29>

 
 EMI29.1
 pure crystallizes thus, melting point 39-4000 # The yield amounts to 433 g C "83.6? * 'from theory) or, ... (OH2) 1, ... 0..OH2 .. .0H2-01t2-1: ... cO ... S-OH, Analysis s 01911390.1; 3 (345, GO) calculated N 4tO5 8 9.28 found U 4.02 8 8.62.



  SxT9prl <.Jj ± 2 While cooling at the start, slowly dropwise added to 427.7 g (* 3 5 molto) of dithlocarbonate dt Sj $ # * dimethyltt sa in a wrinkle and stirred flask, 455.8 The methylmeroaptan obtained is condensed in a strongly cooled trap. After one hour the vacuum is increased to 15 mm Hg and the mixture is further stirred for 36 hours at 15 mm Hg (m 3 5 aolea) 1 "'amino -, - diethylnm1nopropane. more at the
 EMI29.2
 ambient temperature. In this way 703 g of ... (1-d1ethyl-aminopropyl) -thiocarbamate of pure 8-methyl is obtained in the form of colorless liquid, that is to say 98.5% of theory.
 EMI29.3
 



    Analysis: C9H20ON2S (204.34) calcd C 52.90 H 9.87 N 13.71 S 15.69 Found C 52.84 H 9.99 N 13.65 S 15.15 Example 33.



   While cooling with ice-cold water, one introduces dropwise while stirring under vacuum (15 mm Hg) into 61.1 g
 EMI29.4
 (m 0.5 mole) of StSI-dimethyl dithiocarbonate #tu z C. 0.25 mole) of di - (/ 3-aminoethylsulfide). After an hour we gradually warm up to room temperature and
 EMI29.5
 further stirred under vacuum for 24 hours when the reaction mixture solidifies. Then the solid substance is converted into a paste with a little alcohol at -30 C, filtered.

 <Desc / Clms Page number 30>

 
 EMI30.1
 #ur funnel and vacuum sealed. The yield is 3 * thia :: \: 11 t. lne-1Jid-thioa ± \ rba :: o.te of S ...: almost analytical ethyl ...



  Ment ur f * 6 formula
 EMI30.2
 
 EMI30.3
 fondant h. 125 <0 rises; 65 oc. This corresponds to a yield
 EMI30.4
 of 97 theory.
 EMI30.5
 x.ol! 1yle 4.



  By the same proc ,,: é as that described in Example 32o is introduced 30.05 g (a 0.5 mol) of ethylene diamine while rew froi3inonnt strongly with a mixture of ice-cooking salt, and everything is Aritating vigorously in 122.2 g (at 1 mole) of S, St..d1rtethyl dithiocarbonate. 53 ethylene-bia-thiocarbamate of 5-methyl is obtained, which corresponds to a yield of 3.5; of theory. The decomposition point of colorless composa is 140 ° C.



  Analysis: t C6H12N2O2S2 (208.31) calculated C 34.60 to 5.81 N 13.45 3 30.79 found! C 34.89 ü 5.69 N 13.54 8 31.40 ï.r..1 s 755 & (= 0.6 mol) of S, S-dilthyl dithiocarbonate are reacted according to Example 25 under vacuum with 45 g (= 0.3 mol) of 3,3'-diam.nvprop; lmethyls.mine. 37.5 g of K-niethyl-ir, K-dlpropyl-3 3l-bis-thlooarbainat8 from S ...:; ltrle are obtained. This corresponds to 9 'of the theoretical yield.



  Analysis s CllH2; 02N; S (29;, 44)
 EMI30.6
 calculated C 45.04 H 7.90 N 14.33 5 21.80
 EMI30.7
 found 0 44.89 H 7.87 N 14.02 S 20.70 Example 3L6
 EMI30.8
 By cooling initially with ice water we
 EMI30.9
 slowly add dropwise to 488.9 g (m 4 mole), 4.

 <Desc / Clms Page number 31>

 
 EMI31.1
 SySI-dimethyl dithiocarbonate under vacuum (15 mm Hg) while constantly stirring 757 g (= 4 moles) of 1 (2 ', 2'dimethyl) x'3'-diaxoianyi (4')) oxapentycmina After the introduction drop drop by drop of the amine (2 hours) remove the cooled seed and stir at room temperature for a further
 EMI31.2
 A further 36 hours under a vacuum of 50 to 100 mm ES, 1 (9 split methyl mercaptan is captured in a strongly cooled trap.



  The yield of substantially analytically pure S-methyl 1- (2 ', 2diZathyl', 3'dioxolau (')) w OxaPeutYl-5rt'hiocarbamate, of formula:
 EMI31.3
 which is a colorless liquid, amounted to 1053 g. This corresponds to a yield of 100% of theory.
 EMI31.4
 Analysis 1 11H2104NB (263.36) calcd!: C 50.17 H 8.04 N 5.32
 EMI31.5
 found s at 48.94 E 8.05 N 5e39 Xempl..7.



  As in Example 36, 116.0 g (of525 .01.) Of 2.5 ,, .. 'dtxoatetradéoy., Min. Vacuum, are reacted with 64.2 g (#> 0.525 mol) of dithiooarbonata of 8- mdthyle. We obtain 147 g of ,, 8, ... ttroxattrsdoy..4-th, aoaramst of pure S-methyl from foxcnule CH-Oca.) O.ax.c-.c..t.to.c which corresponds to theory 94.5 yield.



  Analysis t 12H250SNS (295.41) Calculated: C 48.79 H 8.53 N 4.74 Found: C 47.65 H 8.18 N 4.90

 <Desc / Clms Page number 32>

   Example 38.
 EMI32.1
 At 36.6 g C. 0.3 mol) of f8'-d.mthye dithioarbonate being in a cooled stirring apparatus, 4 drops are introduced drop while stirring at 0 C under vacuum (15 mm Hg)
 EMI32.2
 29t79 (0.3 mol) of cyclohexylamine. After 2 hours, the cooling is removed and stirred at room temperature until complete separation of the methyl mercaptan (about 27%).

   The reaction mixture then solidifies * It consists of
 EMI32.3
 of 51 µg of aycloixexy.th3.ocaxbame, of pure 8-methyl melting at .10.12 C. The yield thus amounts to 98 # 25) from theory.
 EMI32.4
 



    Example 39.



   As in Example 32, 36.6 g (= 0.3 mol) are reacted
 EMI32.5
 with S, 8'-d1methyl dithiooarbonate empty (15 mm ES) first at 000 with 40 g (0.3 mole) of amanoQetaldehyG.di-ethyl acetal. 61.5 g of ± -methyl H-Xfl-diethoxyethyl-t-iooarbamate of the formula
 EMI32.6
 
 EMI32.7
 as a colorless liquid, Oeoi corresponds to a yield of 98.5 from theory.



  Analyzes aH170, NS (207t3O); calculated N 6.75 found N 6.33 Example 40.



   By the same process as that deorit in Example 25, we
 EMI32.8
 reacts 366 g of 8, S'-dimethyl dlthlooarbonato (3 moles) with 350 g of iaopropoxy-propylamine (= 3 moles). 548 g of iaopropoxyproPY1..thiocarbamate of 3-methyl soue are obtained.

 <Desc / Clms Page number 33>

 colorless liquid form (ie 96% of theory).
 EMI33.1
 Analysis aH1028 (19lt3) calculated: C 50.25 H 8.96 S 7.33 0 16.73 8 16.73
 EMI33.2
 found s 0 49.92 H 8.9 H 7.58 0 17.11 S 17.7 1X;

  ) Jl. 41. In 36.5 g (0.3 mole) of dithiooarbonates of 8,8′-d 4thy- le is introduced with stirring at 0 * 0 dropwise 7.3 g (0.1 mole) of ,, .dimthoxymthy, 4oxa.hepysin.no and the released methylmeroaptan is collected in a cooling trap. After about an hour the pump is connected to water and the reaction is carried out at its tear while stirring at room temperature for about 48 hours.
 EMI33.3
 Almost pure K- (1,1-dlnethylioxy-3-aethyl-4-oxa-heptyl) '- 8-methylyl thiooarbanate of the formula
 EMI33.4
 CH 3 0 1 -GH CH5 cxo CH-CH2-CH-0-CH2-CH2-CH2 -NH-CO-SOH5 CH30 .10e 2-OH-0-CN2-GH2-CH2-NH-cO-BGE is quantitative.
 EMI33.5
 Analysis Cl1H230411S (265.30) calculated C 49.80 H 8.75 N 5.29 found C 50.88 H 9.14 N 5.66 Example 42.
 EMI33.6
 



  30.65 g (3 mol) of NIN-dimethylaminopropylamine are reacted as in Example 24 with 36.5 g (0.3 mol) of di-
 EMI33.7
 8,81-dimethyl thioarbonate in vacuo, first with cooling. 47 g of 8-methyl N, N-dimtthy1am1nopropyl-thiooarbamate of formula
 EMI33.8
 in near pure form, corresponding to a yield of 89% of theory.

 <Desc / Clms Page number 34>

 
 EMI34.1
 



  Analysis 1 C7H160N2S (176.27) calculated C 47.71 H 9.15 N 15.90 8 16.20 Found C 4840 H 9tut, 5 N 15.01 8 18.55 i: c t .., 1.



  The aeniore described in example z.:4, 157.7 g (1.5 moses) of 3-tlilarentylarine with 183.3 g (1.5 "-oLeo) of S dithioarbonate is drained or empty. 3 'dimc'thyle # Aprfea envi- i-oi, 4C hour of cri tution b. The ordinary tonperoturo we get 21 nt do K- (3-thiān-'yntyl) -thiooarbamate of 8-! A <! thyla almost
 EMI34.2
 pure, of the following formula:
 EMI34.3
 Ci: 8-CIâwCFi i-C4-SC This corresponds to a yield of 61 # 51 ,,, 'from theory.



  Analysis t COII13OL82 (179.30) culverted C 40.20 Il 7.32 N 7.82 S 35.75 Found C 40.14 If 7.35 K 7.87 8 36.80 1;,., .-. ,.,., "I ', ..,
 EMI34.4
 In a four-tubular balloon of 5 liters capacity,
 EMI34.5
 ,., J: i d \. 1: d û-1t ± 1tion, a bromine funnel, an internal thermometer and a '' th '') ré1'ri <tro.nt at reflux cooled with a mix
 EMI34.6
 
 EMI34.7
 ! .ÚnH.! Ol ... ne1; e carbonic, we introduce u.Ù \ 1 solution of 264 g (= # 6,6 6 t: .o1ea} of sodium hydroxide in 1400 c3 of water and we 320 g (6.6 mol) of Kdthylnercaptan dissolved in it by introducing it from a cylinder.



  This is added dropwise with vigorous stirring and cooling to 10-x5 C 2370 e of a solution of phos, -; ene in toluene having a phoerene content of 125 g / liter. We aé-ite after making an hour, we separate the phases
 EMI34.8
 and the toluene is distilled through a column to separate it from the
 EMI34.9
 S, S'-dln dithiocarbonate; ethyl9. After distillation of the dithiocrbonate of .8'di, crtth, y.o 168-170C under normal pressure, 296% of pure cosiposi is obtained as a colorless liquid.



  This corresponds to a yield; the 81 has the theory compared

 <Desc / Clms Page number 35>

 with phosgene.



   As in Example 44 is added to a solution of 10 moles of sodium hydroxide and 10 moles of methylmerosptan in 2 liters of water, by means of a metering pump over the space of 3 1/2 hours, 2 liters of toluene, and, in the same temple, 495 g of phosgene are introduced via a side tubing of the introduction tube, via a flowmeter, into the toluene stream. After treatment, 510 g of S, S'-dimethyl dithiocarbon is obtained. This corresponds to a yield of 83% of theory, compared to the mereaptan involved.



    Example. $ 4,
At the tata of a glass reaction tower, provided with a cooling jacket and stirrers and intermediate rest zones in accordance with Figure 4, a tower having 6 om internal diameter and 160 cm high, we introduced by pumping per hour 715 cm3 of an aqueous solution of 3 moles of sodium hydroxide and 3 moles of methyl mercaptan per liter while stirring. At the same time, 80 g of phosgbne dissolved in 400 are introduced at the bottom of the tower cm3 of tou- ene, which becomes suspended by stirring with the streaming solution of meroaptan.

   The temperature inside the tower is kept at +10 C by pumping chilled water around. After adjusting a stationary equilibrium between the two liquid phases, the toluene solution of S, S'-dimethyl dithiocabonate is obtained, leaving through an overflow installed at the top of the tower, solution from which is removed by distillation S, S'-dimethyl dithiooarbonate with a yield of 80% of theory.



   At the foot of the tower, the aqueous solution of sodium chloride obtained is withdrawn with a gear pump and the remains of meroaptan which are dissolved therein are destroyed by means of sodium hypoohlorite.

 <Desc / Clms Page number 36>

 
 EMI36.1
 



  Example .46.



   In a 5-liter four-necked flask fitted with a stirrer, a dropping funnel, an internal thermometer and a reflux condenser (with cooling with methanol-carbon dioxide snow) a solution is placed in advance. of 400 g of sodium hydroxide (about 10 moles) in 600 cm3 of water.



    Into it is slowly introduced 620 g of ethylmeroaptan and then added dropwise at a temperature of about 0 + 5 C while cooling and vigorous stirring 3260 g of a solution of 480 g of phosgene (about 4, 86 moles) in
 EMI36.2
 S780 g of toluene. After addition of the phosgene solution, the mixture is stirred for an hour afterwards, the phases are then separated and the toluene is removed from the 8031 diethyl dithiooarbonate by distillation through a column. When the residue is distilled. obtains 616 c of pure ester in a colorless liquid form having a boiling point of 78 C at 15 mm Hg. This corresponds to a yield of 84.4% of theory with respect to phosgene.



    CLAIMS.
 EMI36.3
 



  I.- Process for the preparation of organic 3.atoyanates, characterized in that a) is heated for a short time under
 EMI36.4
 reduced pressure to 100 - 600 "0 an aloylated tater of N-aloo-yl- or N-ary1thiooarbamic acid ot then immediately cools the cleavage products below 80 C and separates the liquid phase from the gas phase, or in what b) we heat a
 EMI36.5
 ester of N-alkyl- or N-arylthiooaroamic acid in an inert solvent and isolates the istocyanates formed by separating them by dictilation.



  2. A process according to claim 1, characterized in that an 8-methyl ester of N "alooyl- or N-aryl-thiooarbamic acid is used.

 <Desc / Clms Page number 37>

 



   3. A method according to claims 1 and 3, characterized in that heating to 160 - 400 C under reduced pressure.



    @
4. A process according to claims 1a ?, characterized in that the heating takes place at a reduced pressure of 0.1 to 100 mm Hg.



   5. A process according to claim 1, characterized in that the heating of the aloyl ester of N-alco-yl- or N-arylthiocarbamic acid is carried out in a solvent which boils a temperature of 160 to 360 C at Mud at a pressure of 0.1 to 100 mm Hg.



   6. A process according to claims 1 to 5 characterized in that benzyl benzoate is used as solvent.



   7. A method according to claims 1 to 5, characterized in that the solvent used is dibutyl phthalate.



   8.- Process for the preparation of 6-esters of N-substituted thiocarbamic acid by reaction of primary amines with S, S'-dieaters of dithiocarbonic acid, characterized in that the partners of reaction in as exactly equivalent amounts as possible and in that the mercaptan which forms during the reaction is constantly removed.



     9. A method according to claim 8, characterized in that, to remove the mercaptan, the reaction is carried out empty us.



   10. A process according to claim 8, characterized in that the mercaptan is removed from the reaction mixture by entraining it by means of a stream of inert gas
11. A process according to claim 8, characterized in that the S, S'-diester of dithiccarbonic acid is used as S, S'-dimethylated dithicaarbonic acid.



   12.- Process for the preparation of S, S'-diesters of dithio acid. carbonic acid, characterized in that a solution of a meroaptan in an aqueous solution of alkali hydroxide is reacted with a solution of phosgene in an inert solvent which is not used.

 <Desc / Clms Page number 38>

 
 EMI38.1
 # bit * with water while mixing 1ntenoéQent the phoeaa with dee ttmpdraturee inrtr1.euruo at 30C ..



  13. A process follows claim 12 for the. continuous preparation of dieatero of th1oonrbonic acid. oarac-1 tÓrlg (in this case JUDO a vertical reaction tower is made r / {l, '1 a uyueuve solution of an alkali hydroxide of a mer- cartun with the rsoxui ion of phosgene in an inert solvent no
 EMI38.2
 miscible 1.1. water in counter-current with intense mixing of
 EMI38.3
 phatJQ8 ü temperatures lower than 30?.



  14. A process according to claims 12 and 13, characterized in that toluene is used as the solvent for phosgene.



  15 .... Apl, arail for read ease of implementation of the following process leu rcvoz3dicatirins 12 and 13. characterized in that the rt-action tower (1) provided with the cooling jacket (20) with 3t ": itator at p.11ettca (2) had the two supply conduits
 EMI38.4
 (9) and (12) as well as the two discharge pipes (13) and
 EMI38.5
 (16) t 2.a conduct ws.L. '.;: ;; ÂA (9) formed by the connection of conduits (4) and (21) leading through conduit (8) through 1 cooler (5).