DE1568772A1 - Process for the preparation of sulfamic acid derivatives - Google Patents

Description

Process for the preparation of sulfamic acid derivatives Di. Invention relates to a process for the preparation of sulfamic acid derivatives.

The inventive method for producing an N-zubsrtituierten Suflaminsäurederivate is marked by the fact that sulfur triezyd in the dam state with a primary secondary amine in the vapor state at a temperature between 130 ° and 200 ° C is implemented. The defaulted Amie are the cyclealkylamines and in particular Zyklehexylamine and Aklyamine such as e.g.

Iseprepylamine, isabutylamine and iseamylamine.

The amine / sulfur trioxide ratio is preferably about 2 | 1, namely that to obtain the corresponding, in the subsequent description as "the amine salt" denoted quaternary N-added Ammenimmeulfamäts required Melting ratio, which is advantageously not less than 1.5: 1 and between 1.95 : 1 and 3: 1 zein can The amine salt obtained with Zyklehexylamin is Zyklehexylammenium-N-Cyclohexylsulfamat $ C5H11NH3. SO3NHC5H11.

The amine can be added using conventional chemical methods be converted into an acid or metal salt such as sodium or calcium salt.

The translation takes place preferably in the presence of a gaseous diluent instead, which is inert under the reaction conditions. Under the suitable thinning agent fall trek air and nitrogen gas.

German reaction system temperatures are different, but preferably 160-200 ° C and especially 170-190 ° C or 175-180 ° C and can be maintained controlled by the concentratino of the reactants and the speed with which they can come into contact with each other.

The reactants become, for example, intimate with one another in a vortex scene connected, this vortex scene is formed or promoted with the help of a cebre will be comb.

Because the dilute reactants swirled in the durohum State to be brought together in Kentakt. Lecal overheating can be alleviated will.

The process product according to the invention is in terms of color and Improved yield. This is not the only reason why the procedure is used at a. Molar ratio carried out by about 2 1 1 of amine and sulfur trioxide, because on dese wise the It is necessary to use the amine or cyclohexylamine, for example is reduced to a minimum, but also because it creates a free-flowing powder is obtained that is not moistened by excess liquid amine. Even the color of the preduct obtained with such a ratio is better than at efnsm higher milk ratio.

The lower temperatures will cause considerable amounts of cyclohexylammonium sulfate or the appropriate oil fate with other amine reactants.

When implemented at temperatures of 130 ° to 200 ° C and insbesendere Smaller amounts of sulphate are obtained from 170 ° to 190 ° C.

The invention is illustrated using the example below.

Example 1 Sulfur trioxide and cyclohexylamine - both in steam - have been changed in the system shown in the attached drawing. This system has a Remktiengsäß 1, two nozzles 1 and 3 in the upper part are provided through which the reactant participant vapors are introduced. These Düzen X and 3 are grounded in such a way that the two steam flows flowing through them kenvergieren. A fan 4 is grounded in the Reaktiemagefäß that it is Zene swirled air can form on the tent, on which both steams pinch together: A thermal element 6 has also passed away in the scene, in which one both steams unite. The lower end of the reaction vessel 1 is pierced itt two large containers ("Heaschemmen") 7 and 8 in connection, weven each with a receiving container 9 or 10 for the preduct and the container 8 with a gas gauge 11 is given away.

Bin Strem from Zehwefeltriexyddempf in Stiokzteff was through at 100 ° C the nozzle 2 and a stream of Zyklehexylamimdampf in Stieksteff was at 100 ° C through the nozzle 3 in the sit älife of the blower 4 formed by swirling air imported. The delivery speed of the Zekwefeltriexyde was about 1.7g each Liters of Ztieksteff pre minute, while the Zyklehexylamin at one rate ven about 4.21g per 3 Liier Sticksteff pre minute and the molar ratio Cycichexylamine 1 sulfur trioxide s 1 1 was The reaction temperature was 170-180 ° C. Then the eddy current flowed through the reaction vessel 1 into the containers 7 and 8 and the reaction product was collected in collecting tanks 9 and 10.

After the past had taken an hour to complete, we were 306g of its solid preduct was obtained. Crystals and filtration were carried out from the solid product 245 g of Zyklchexylammenium-N-Zylkehexylaulfamnt (one exercise ven 69%), 12.3 g N, N'-Dimyklekexylzulfonamid and 48.7 s Zylkehexylammoniumzulfat hold.

Example 2 Am stream from sulfur trioxide vapor in Silckzteff and a Cycleshexylamino vapor streams were combined as in Example 1. The feed rate of the sulfur trioxide was about 1.48 g per liter of Stickzteff per minute, while the Zyklehexylamin at a speed of around 3.65 g jo 3 liters of Stieksteff was supplied per minute, with dos mel ratio cyclohexylamine 1 sulfur trioxide was 2: 1. Sewehl der Ztrem from sulfur trioxide and Stieksteff than after the strum of Zyklehexylamin and Stecksteff was at eimeg temperature from 100 ° C introduced into the reaction vessel. The reaction temperature was 170-180 ° C C. Then the eddy currents of the reaction participants poured into the large container 7 and 8 and the reactantspredu @ t was collected in collecting containers 9 and 10.

After the pass took an hour, it became 306 g of a solid Received preachings. The solid product was obtained by means of Krimtall rights and Filtratien 245 g Zykichexylammenum-N-Zyklehexylsuflamat (an extension of 80%), 12.8 g N, N'-Dizyklehexylsulfonamid and 18.7 g of cyclohexylaminesulfate.

The Zyklehexylammnium-N-Zyklehexylsufamat (245 g) was with a Solution of 35.2 g of sodium hydroxide in 400 ml of water. By evaporation and Crimping of the solution obtained was 160 g of sodium N-cyclohexyl sulfamate to cool off.

Example 3 Bin Strem plus sulfur triexyl vapor in Sticksteff and a stream of iseamylamine vapor in Stieksteff is poured into the reaction vessel at 100 ° C make example 1 through the nozzles 2 or 3 in the vortex airzome introduced with the fan 4 was to be formed. The speed of feeding the sulfur triexylde was about 1.48 g per lier Sticksteff per Mimmte and the feed speed The iseamylamine was about 3.2 g per 3 liters of Sieksteff per Mimmte, $ while that Mel ratio iseamylamide 1 sulfur trioxide was 2 o t. The reaction temperature was 170-180 ° C.

The eddy currents of the Beaktiensteilnekmer rushed to the front Containers 7 and 8 and the Reaktiemspredmkt was melted in the storage containers 9 and 10.

After the past thundered for an hour, 260 g became solid predakts collected. Crystallism and filtration resulted in the solid Product 245 g Iseamyiammeniun-N-Iseamylemlfamat, 4 g N, N'-Dileeamylealferamid und 11 g of iseamylammium sulfate were obtained.

The iseamylammenium-N-iseamylsulfamate (245 g) is said to be with a bucket of solution cooked from 38.5 g of sodium hydroxide in 500 ml of water. By evaporation and crystallization 150 g of sodium N-iseamylenelfamate were cooled from the resulting solution.

Example 4 This example blames the aftereffect on the color of the preduct, if the neophytes amine: Zehwefeltriexyd 3 1 1 exceeds.

This example was carried out in the plant according to Example 1. Three tests were carried out according to Example 1. only that now the centering of sulfur trioxide and Zyklehexylandine are those in Table 1 shown were TABLE 1 Melting ratio of feed rates Zyklehexylmmin: SO3 SO3 Zyklehexylamin S 1 1 4.2g in 3 1 Sticksteff / 1.7 g in 1 1 min Sticksteff / min.

3: 1 4.2g in 31 Sticksteff / 1.1g in 0.5 1 min. Sticksteff / min.

4: 1 4.2g in 3 X Sticksteff / 0.85g in 0.3 1 min. Sticksteff / min.

The two fabric values of the crude reactants were given as 4.5% strength W / V solutions in water and 4.5% W / V solutions in aqueous sodium hydroxide determined and measured in each fur in a two-cell cell of a Levibend colorimeter and after all the insoluble substances, which essentially consist of N, N'-dicyklehexylsulfenamide passed, discontinued. The results obtained are from the follow-up Table 2 2 can be seen.

TABLE 2 Test of Mel ratio in a two-cell cell with a Levibend cyclchexylamoine Farbenmessere measured Frabwerie 1 SO3 4.5% w / v solution 4.5% w / v solution in Water in aqueous sodium hydroxide R G 1 R G 1 2: 1 0.2 0.8 - 0.1 1.0 -2 3: 1 0.3 1.0 - 0.1 1.2 -3 4: 1 1.0 3.4 0.1 3.6 3.0 0.1 R = red G = yellow P r blue Die marked increase in the color values of the crude reactant product at a mel ratio the participants in the reaction of i 1 1 (experiment 3) can be clearly seen from Table 1.

The reaction temperatures during Trials 1, 2 and 3 were respectively 17-180 ° C, 130-135 ° C and 1050 C. Although the temperatures in the three experiments were different, it was found that the use of lower reaction temperatures such as temperatures below 190 ° C not. to worsen the color of the reactants product but rather to improve the color of the preduct.

Example 5 This example illustrates the effect of more de-gassed Return temperatures. The performance described in Example 1 became slightly changed by attaching a cooling jacket to the reaction vessel n became.

Since the cooling liquid duroh the variable speed A cooling jacket was used to regulate the reaction temperature disregarded. Then the experiment described in Example 1 was carried out at 45 ° C, 100 ° C, 1400 C and 1800 C controlled temperature repeated; the test results obtained are shown in Table 3.

TABLE 3 Analysis of the Reaktiemapreduktm Reaktienztemperater N, N'-Dizyklehexal- Zyklehexyl- Zyklehesulfonamid in% ammenium- xylammo-N-Zykle- niumsulhexylsulfa- fat in * mat in% 450 c 3 45 53 100 ° C 2 52 49 1400 C 3 55 46 1800 C 3 70 25 153 g of the product obtained in an experiment at 1800 ¢ srn with 26 g of sodium hydroxide, dissolved in 700 cem of water, mixed and the mixture became to obtain the Zyklehexylamine cooked. If the cyclohexylamine was distilled off, the aqueous distillate became Extracted five times with 1,1,2-Trichlerwthan to obtain N, N'-Dixyklehexylzulfenamid.

Then the 77 g of sodium N-Zyklehoxyizulfamat @mthhaltende was purified aqueous solution in addition to their kensentratien, until the kensentratien of the Sodium N-Cycichexylzulfamet was 35% w / w upon which it was allowed to crystallize. After filtration and Treakmung 50 g of rhyme sodium-N-Zyklehexylsulfamat were obtain.

A second indication was given by the Wiederkemnentratien der Mother liquor obtained from the eraten Krietallieierung who on the kemaentrierte Lye crystalline lies.

The yields shown in Table 3 were determined by the amnlyysis of the Reaktimmapredukte determined after its treatment with water, eralchtlieh is that di. Sum of the yields in some experiments exceeds 100%.

It is possible that if the implementation is incomprehensible, part of the with added cyclohexylamines and sulphuretriexides adserbed in the reaction product or is kept on other pasture and that the reactantsprdact after addition ven Waseer mmaetzt any remaining Zchulfeltriexyd in Zehwereleäure, which centralized by remaining Zyklchexyauin with the formation of Zyklehexylammeniumsulfat will. This seems to be the explanation of the $ 10 staggering sum. i.e. the Total values over 10% are probably the result of the increase in the Melekulargewlcht after this the Reaktienspredukt treated with water and the remaining in the Reaktienspredukt Sulfur trioxide has been converted into sulphurous acid.

Claims

Claims (1)

Claims 1. Process only production of N-substituted Sulkamat, characterized in that sulfur trioxide in the vapor state with a primary or secondary amine in the vapor state at a temperature of 120 ° -200 ° C 0 is implemented, 1. Ancestors according to Amspruch 1, characterized in that the therein is primary cyclic alkylamine. 3. The method according to claim 2, characterized in that the cycloalclamine Is cyclohexylamine. 4. The method according to claim 1, characterized in that the amine is primary iselakylamine. 5. The method according to claim 4, characterized in that the isealkylamine Is isaprepylamine, isebutylamine, or iseamylamine. 6. The method according to any one of the preceding claims, characterized in that that the meling ratio A @ min / Gekwefeltriexyd 1.5 5 - 3 1 is. 7. The method according to one of the preceding claims, characterized in that that the amine / sulfur trioxide ratio is 1.95: 1-3 3 1, 8th, Method according to claim 7, characterized in that the meling ratio ii is essential 2 1 1 is. 9. The method according to one of the preceding claims, characterized by that the reaction is carried out in the presence of an inert gaseous diluent vird. 10. The method according to one of the preceding claims, since duroh gekennseichnet, that the reactants are brought into contact with one another in their vortex will. 11. The method according to claim 10, characterized in that the turbulence with the help of a blower. 12. The method according to one of the preceding claims, characterized in that that the reaction takes place at temperatures ven 160-200 ° C. 13. Verfakren according to claim 12, characterized in that the Umsetmmg takes place at temperatures of 170 - 190 ° C. 14. Procedure according to one of the previous speeches, thereby marked, that the N-substituted sulfamate is reddened into a metal breath. 15. The method according to one of the preceding claims, which is identified that the reaction temperature by monitoring mag or control of the Kemaentration Reaction participants and the speed with which the Reaktiensteilnehner have been crashed into contact with each other. lee rs ei t e