(Hive Addict)
10-02-03 08:34
No 462238
(Rated as: excellent)
I would have posted this in the OTC alkyl tosylates thread in Novel, but a) I want to get more attention by separate posting
and b) tosyl chloride / bromide are of much broader synthetic relevance then the production of tosylates, finally c) that attention thing again. (forgive... I'm diagnosed with ADD 
)toluenesulfonic acid chloride from toluenesulfonic acid, sulfur and chlorine
In the preface they say halogens in general, not only chlorine... I think it's a little easier to work with Br2... but then again, how do you thoroughly dry Br2 made from KBr/H2O2/H2SO4 without having to handle its vapors ? Well, anyway, here comes the juicy part - and it really kicks any diazo method's ass !
Example 1, with CCl4
250g toluenesulfonic acid and 50g sulfur are digested in CCl4 and treated with Cl2 under continuous stirring. The evolution of heat is prevented by external cooling. The sulfur gradually dissolves while at the same time HCl and H2SO3 escapes. After finished Cl2 uptake the reaction mixture is treated with dH2O, on the one hand to decompose left over S2 Cl2, on the other hand to remove the dissolved HCl/H2SO3 . The CCl4 solution leaves 250g nearly pure toluenesulfonic acid chloride after vaporization of the solvent, which corresponds to a yield of 90%. If one starts with pure toluenesulfonic acid, the final TsCl has a m.p. of 68°C.
Example 2, neat.
5 parts by weight of toluenesulfonic acid, that has to be completely free of water and sulfuric acid and under these conditions is in a slightly fluid form because it has extraordinarily little inclination to crystallize, is mixed with one part by weight sulfur and treated with chlorine under good stirring. Temperature is appropriately held a few degrees above room temp, to favour Cl2 uptake. After finished chlorination the process is interrupted and the tosylchloride is freed from small amounts of impurities like S2Cl2 by the known methods.
Patent DE499052 <__ I love my country
--psyloxy--
(Official Hive Translator)
10-02-03 11:32
No 462257
And that turned out to bee so simple... This is precisely THE preparation of TsCl i've been searching for a very long time!
Double wow, Psyloxy!!! A kitchen chemist's treasure you've found.
Antoncho
(Hive Bee)
10-02-03 15:43
No 462272
This group of compounds comprises methylbenzenesulfonic acids (toluenesulfonic acids), [25231-46-3] , C7H8O3S, Mr 172.20, methylbenzenedisulfonic acids (toluenedisulfonic acids) C7H8O6S2 , Mr 252.26, dimethylbenzenesulfonic acids (xylenesulfonic acids) [58723-02-7] , C8H10O3S, Mr 186.23, and their derivatives.
Production. The sulfonation of toluene is accomplished more easily than that of benzene and is accompanied by less sulfone formation. Low temperatures favor o-substitution; m-substitution occurs only to the extent of about 2 – 3 %. At temperatures around 100 °C the ratio of o- to p-substitution is about 3 : 7. The sulfuric acid concentration has a strong influence on the isomer ratio [4]. Surprisingly, almost 100 % p-substitution is obtained at –10 °C if sulfur dioxide is used as the solvent [5].
At a sulfonation temperature of 100 °C and a sulfuric acid concentration of 97.4 %, 31 % m-substitution is achieved [6]. Through rearrangement at 140 – 200 °C the concentration of m-toluenesulfonic acid rises to about 46 % [7][8]. If this is followed by hydrolysis with steam at 170 – 200 °C, the concentration of m-isomer rises to more than 90 % [9].
Isolation from the Mixture. p-Toluenesulfonic acid can be crystallized from 66 – 71 % sulfuric acid, or from concentrated hydrochloric acid at temperatures below 0 °C [10]. Then, according to the reaction conditions of the preceding sulfonation, the o- or m-toluenesulfonic acid can be obtained from the mother liquor. If the compounds are required to be very pure, the route via the toluidines (diazotization and reaction with sulfur dioxide) is preferred [47].
2,6-Toluenedisulfonic acid can be obtained by adding 65 % oleum to the sulfonation reaction mixture while the temperature is below 100 °C and then raising the temperature to 125 °C. In 90 % sulfuric acid at 190 °C, 64 % of the 2,4-toluenedisulfonic acid rearranges to 3,5-toluenedisulfonic acid. The 3,5-isomer is isolated from hydrochloric acid solution at –15 °C [11].
Uses. Toluenesulfonic acids are used as isomer mixtures, or as mixtures with xylenesulfonic acids; they serve as solubilizers, as acidic catalysts, and as additives for detergents [12]. They are used as intermediates in the production of cresols and sulfobenzoic acids.
2-Methylbenzenesulfonic Acid [88-20-0] , o-toluenesulfonic acid, C7H8O3S, Mr 172.20, flaky crystals (dihydrate), mp 62.1 °C.
Produced together with 4-methylbenzenesulfonic acid by sulfonation of toluene with 96 % sulfuric acid at 40 °C, or preferably with 1 mol of chlorosulfuric acid at 0 to –10 °C. Used to produce o-sulfobenzoic acid.
2-Methylbenzenesulfonyl Chloride [133-59-5] , C7H7ClO2S, Mr 190.65, bp13 mbar 126 °C, mp 15.5 °C. Manufactured by treating toluene with chlorosulfuric acid at temperatures not exceeding 3 °C, forcing the reaction mixture into ice, siphoning off the water, and centrifuging 4-methylbenzenesulfonyl chloride. Used in the production of toluenesulfonamide.
2-Methylbenzenesulfonamide [88-19-7] , C7H9NO2S, Mr 171.22, mp 156.5 °C, is obtained by treating 2-methylbenzenesulfonyl chloride with aqueous ammonia (d 0.910). Purified by fractional precipitation: hydrochloric acid is added to a solution which has been rendered alkaline with sodium hydroxide; the impurities are precipitated first. Used in the manufacture of saccharin (® Sweeteners - 6.4. Saccharin).
3-Methylbenzenesulfonic Acid [617-97-0] , m-toluenesulfonic acid, C7H8O3S, Mr 172.20. The pure acid can be obtained from m-toluidine. Isomer mixtures with m-isomer concentrations of more than 50 % are obtained from toluene sulfonation mixtures by bubbling in toluene vapor at 180 – 205 °C [13] , see also [9]. Used to manufacture m-cresol (® Cresols and Xylenols).
3-Methylbenzenesulfonyl Chloride [1899-93-0] , C7H7ClO2S, Mr 190.65, bp29 mbar 146 °C, mp 11.7 °C. Obtained from m-toluidine according to [33]. Yield: 71.2 %.
3-Methylbenzenesulfonamide [1899-94-1] , C7H9NO2S, Mr 171.22, mp 103 °C.
4-Methylbenzenesulfonic Acid [104-15-4] , p-toluenesulfonic acid, C7H8O3S, Mr 172.20, mp 38 °C, monohydrate mp 106 °C, trihydrate mp 93 °C, bp26.3 mbar 140 °C.
Production. According to the process of Allied Chemical and Dye Corp. [14] , boiling toluene is sulfonated with 90 – 95 % sulfuric acid. Evaporating toluene is condensed, separated from water, dried, and recycled. A mixture with a p-isomer content of 75 – 85 %, an o-isomer content of 10 – 20 %, a m-isomer content of 2 – 5 %, and less than 1 % of sulfuric acid is present at the end of the reaction. There is very little sulfone formation. The process can also be performed continuously in a vertical reactor [16].
The reaction of toluene in a continuous process with sulfur trioxide as sulfonating agent allows toluenesulfonic acid to be generated with high para selectivity and with the advantage of few byproducts and low waste-gas emissions [15].
For some purposes, for example, for use as an acidic catalyst or in cresol manufacture, the crude toluenesulfonic acid obtained according to the above processes does not have to be purified. Purification is possible by crystallization from 66 % sulfuric acid or via the barium salt.
Uses. The applications of 4-methylbenzenesulfonic acid include the manufacture of 4-formylbenzenesulfonic acid, p-sulfobenzoic acid, 2-chlorotoluene-4-sulfonic acid, and 4-(chloromethyl)phenylmethanesulfonic acid.
4-Methylbenzenesulfonyl Chloride [98-59-9], tosyl chloride, C7H7ClO2S, Mr 190.65, bp25 mbar 138 – 139 °C, mp 69 °C. Formed as a byproduct in the manufacture of 2-methylbenzenesulfonyl chloride, from which it can be separated by remelting several times under water.
This compound is used in the production of sulfonamides, arylides, nuclear-substituted toluenesulfonyl chlorides, 4-(chloromethyl)benzenesulfonyl chloride, and p-toluenesulfinic acid. The tosylation of hydroxyl groups, i.e., their esterification with p-toluenesulfonyl chloride, serves to protect these groups; this method is employed particularly often in the chemistry of natural substances [17].
4-Methylbenzenesulfonamide [70-55-3], C7H9NO2S, Mr 171.22, mp 137 °C, dihydrate mp 105 °C, weak acid, soluble in aqueous alkali. Produced from the sulfonyl chloride with aqueous ammonia. Used in the production of chloroamines, e.g., chloramine T and dichloramine T (® Chloroamines).
Methyl 4-Methylbenzenesulfonate [80-48-8], C8H10O3S, Mr 186.23, bp17 mbar 168 – 170 °C, mp 28 °C, is obtained from the chloride of the acid by reaction with methanol; important alkylating agent.
Ethyl 4-Methylbenzenesulfonate [80-40-0], C9H12O3S, Mr 200.26, bp0.4 mbar 137 – 139 °C, bp12 mbar 165 – 166 °C, mp 34 °C, is obtained from the sulfonyl chloride and ethyl alcohol at –5 to 0 °C after addition of 45 – 50 % sodium hydroxide solution [18]. Used as an alkylating agent and as a plasticizer.
4-(Chloromethyl)benzenesulfonic Acid [46062-27-5], C7H7ClO3S, Mr 206.65, hygroscopic crystals, is obtained at a yield of 90 % through the action of chlorine on sodium 4-methylbenzenesulfonate in the presence of dichlorobenzene [19]. Used in the manufacture of surfactants.
4-(Chloromethyl)benzenesulfonyl Chloride [2389-73-3], C7H6Cl2O2S, Mr 225.09, mp 64 – 65 °C, bp20 mbar 183 – 195 °C, is obtained by treating 4-methylbenzenesulfonyl chloride with chlorine in the presence of PCl5 at 120 – 140 °C.
Methyl 4-(Chloromethyl)benzenesulfonate [89981-68-0] , C8H9ClO3S, Mr 219.67, is used as a quaternizing agent. Reactions with tertiary amines, e.g., trimethylamine, give sulfobetaines with fungistatic properties [20].
4-(Acetylaminomethyl)benzenesulfonyl Chloride [39169-92-1] , C9H10ClNO3S, Mr 247.70, mp 95 – 97 °C, is obtained from N-acetylbenzylamine and chlorosulfuric acid [21].
4-(Acetylaminomethyl)benzenesulfonamide [2015-14-7] , C9H12N2O3S, Mr 228.27, mp 177 °C (from water or aqueous alcohol), is produced from the sulfonyl chloride with aqueous ammonia at 15 and 70 °C; yield 80 %. It is an important intermediate in the manufacture of 4-(aminomethyl)benzenesulfonamide.
4-Methyl-1,3-benzenedisulfonic Acid [121-04-0] , C7H8O6S2 , Mr 252.26, is a viscous oil. Obtained by additional sulfonation of the o- and p-toluenesulfonic acid mixture with 66 % oleum at 125 °C. Used in the manufacture of 4-formyl-1,3-benzenedisulfonic acid, 4-carboxy-1,3-benzenedisulfonic acid, and 4-methylresorcinol.
4-Methyl-1,3-benzenedisulfonyl Chloride [2767-77-3] , C7H6Cl2O4S2 , Mr 289.16, mp 56 °C, is produced from toluene and chlorosulfuric acid at 120 °C [22]. Addition of phosphorus pentoxide raises the yield [23].
4-Methyl-1,3-benzenedisulfonamide [717-44-2] , C7H10N2O4S2 , Mr 250.30, mp 190 – 191 °C.
2,4-Dimethylbenzenesulfonic Acid [88-61-9] , m-xylenesulfonic acid, C8H10O3S, Mr 186.23, dihydrate: mp 57 °C, prisms or flakes. Produced by sulfonating m-xylene with concentrated sulfuric acid; the acid is precipitated by dilution with water. Of the three isomeric xylenes, m-xylene is the one most easily sulfonated. The ease of sulfonation decreases in the order m>p>o, whereas the ease of hydrolysis increases in the order o<m<p. m-Xylenesulfonic acid is hydrolyzed at 180 °C. Used in the production of nitroxylenesulfonic acid, chloroxylenes, and chloroxylenesulfonic acids.
2,4-Dimethylbenzenesulfonyl Chloride [609-60-9] , C8H9ClO2S, Mr 204.68, mp 34 °C.
2,4-Dimethylbenzenesulfonamide [7467-12-1] , C8H11NO2S, Mr 185.25, mp 138 °C.
2,5-Dimethylbenzenesulfonic Acid [609-54-1] , C8H10O3S, Mr 186.23, mp 48 °C, bp 149 °C (cathode vacuum), is soluble in chloroform. The dihydrate, mp 95 °C, is obtained by sulfonating p-xylene with 93 % sulfuric acid and removing the water by distillation [24]. Used in the production of 2,5-xylenol.
2,5-Dimethylbenzenesulfonyl Chloride [19040-62-1] , C8H9ClO2S, Mr 204.68, mp 25.5 °C, bp29 mbar 152 – 153 °C.
2,5-Dimethylbenzenesulfonamide [6292-58-6], C8H11NO2S, Mr 185.25, mp 148 °C.
4-Ethylbenzenesulfonic Acid [98-69-1], C8H10O3S, Mr 186.21, is produced by sulfonating ethylbenzene with sulfuric acid. It is separated from the isomers via the aniline salt [25]. Used in the production of p-ethylphenol.
4-(2-Bromoethyl)benzenesulfonic Acid [54322-31-5] , C8H9BrO3S, Mr 265.13; S-benzylisothiuronium salt, mp 149 – 150 °C. The acid is obtained by sulfonating 1 mol of (bromoethyl)benzene with 1.1 mol of SO3 in methylene chloride [26] , see also [27] , [28]. The potassium salt is obtained by treating the sulfonyl chloride with potassium carbonate in water [29].
4-(2-Bromoethyl)benzenesulfonyl Chloride [64062-91-5] , C8H8BrClO2S, Mr 283.58, is produced from 2-(bromoethyl)benzene and chlorosulfuric acid at temperatures not exceeding 25 °C [30]. Used in the production of 4-vinylbenzenesulfonic acid.
4-(2-Bromoethyl)benzenesulfonamide [5378-84-7] , C8H10BrNO2S, Mr 264.15, mp 185.5 – 186 °C.
4-Vinylbenzenesulfonic Acid [98-70-4] , C8H8O3S, Mr 184.21; p-toluidine salt, mp 182 – 183 °C, is obtained in the form of the potassium salt from 4-(2-bromoethyl)benzenesulfonic acid with methanolic KOH [51] or from 4-(2-bromoethyl)benzenesulfonyl chloride with alcoholic KOH [52]. The monomer can be stabilized by adding 0.5 – 5 % of sodium nitrite [53].
4-Vinylbenzenesulfonic acid has been proposed for copolymerization with acrylonitrile to improve the dyeing properties of the fibers [54] and as a starting product in the manufacture of polymeric styrenesulfonic acid [51] , [52].
4-Vinylbenzenesulfonamide [2633-64-9] , C8H9NO2S, Mr 183.23, mp 138 – 139 °C [55].
4-tert-Butyl-2,6-dimethylbenzenesulfonic
2,3-Dihydro-1H-indene-5-sulfonic acid [40117-41-7] , C9H10O3S, Mr 198.24, is obtained by precipitation as a sodium salt, after 2,3-dihydro-1H-indene and concentrated sulfuric acid have been reacted at 150 °C [57]. At low temperatures mainly 1H-indene-4-sulfonic acid is formed. 1H-Indene-5-sulfonic acid has been proposed as a starting material for the manufacture of sulfonylureas with hypoglycemic effects [58].
2,3-Dihydro-1H-indene-5-sulfonyl Chloride [52205-85-3] , C9H9ClO2S, Mr 216.69, mp 49 °C, bp21 mbar 180 °C, is obtained by treating the sodium salt of 1H-indene-5-sulfonic acid with PCl5 , or by the reaction of 2,3-dihydro-1H-indene and chlorosulfuric acid at 0 – 15 °C, pouring onto ice, and extracting with chloroform [59].
2,3-Dihydro-1H-indene-5-sulfonamide [35203-93-1] , C9H11NO2S, Mr 197.26, mp 135 °C.[u]
(Hive Bee)
10-02-03 15:47
No 462274
[4] H. Cerfontain, F. L. J. Sixma, L. Vollbracht, Recl. Trav. Chim. Pays-Bas 82 (1963) no. 7, 659 – 670.
[5] Tennessee Corp., Patent US2841612 , 1956.
[6] V. S. Patwardhan, R. E. Eckert, Ind. Eng. Chem. Process Des. Dev. 20 (1981) no. 1, 82 – 85.
[7] A. A. Spryskov, V. A. Kozlov, Khim. Khim. Tekhnol. Alma Ata 1962 12 (1969) no. 2, 166 – 169 (1969).
[8] A. A. Spryskov, V. A. Kozlov, Khim. Khim. Tekhnol. Alma Ata 1962 12 (1969) no. 7, 900 – 902 (1969).
[9] Koppers, Patent BE844860 1975 (US Appl. 602768, 1975). = Patent US4112118
[10] A. A. Spryskov, Khim. Khim. Tekhnol. 4 (1961) no. 6, 981 – 984.
[47] H. Meerwein et al., Ber. Dtsch. Chem. Ges. 90 (1957) 846.
[11] T. I. Potapova, A. A. Spryskov, Khim. Khim. Tekhnol. 10 (1967) no. 8, 885 – 887.
[12] Witco Chem., Patent DE1812708, 1968.
[13] Taoka Dye MFG., JP 68/22861, 1964.
[33] Matsuyama Sekiyuka, JP 52133945, 1976.
[14] Allied Chem. & Dye Corp., Patent US2362612 1942.
[16] Standard Oil Develop. Co., Patent US2540519, 1946.
[15] Hoechst, Patent DE2837549, 1987.
[17] Org. Synth., Coll. Vol. III (1955) 366.G. Storck, R. Borch, J. Am. Chem. Soc. 86 (1964) 937.
[18] M. J. Morgan, L. H. Cretcher, J. Am. Chem. Soc. 70 (1948) 375.
[19] Phillips Petroleum Co., Patent US2678947, 1949.
[20] BASF, Patent DE1157629, 1962.
[21] F. H. Gereim, W. Braker, J. Am. Chem. Soc. 66 (1944) 1459.
[22] W. Herzog, Angew. Chem. 39 (1926) 728.
[23] Sankyo Kasei Co., JP 67/13937, 1965.
[24] H. Meyer, Justus Liebigs Ann. Chem. 433 (1923) 333.
[25] Sugai Chemical, JP-KK 52136144, 1976.
[26] Dow, Patent US2821549, 1954.
[27] Toyo Soda MFG, JP-KK 55031059, 1973.
[28] Toyo Soda MFG, JP-KK 55064565, 1978.
[29] Du Pont, Patent US2837500, 1953.
[30] G. E. Inskeep, J. Am. Chem. Soc. 69 (1947) 2237.
[51] R. H. Wiley, J. Am. Chem. Soc. 76 (1954) 720.
[52] R. H. Wiley, S. F. Reed, Jr., J. Am. Chem. Soc. 78 (1956) 2171.
[53] Du Pont, Patent US2822385, 1955. and Patent US2822386
[54] Dow, Patent US2913438, 1955.
[55] R. H. Wiley, C. C. Ketterer, J. Am. Chem. Soc. 75 (1953) 4520.
[56] Mitsubishi Petro-Chem., JP 70/36498, 1967.
[57] W. Borsche, M. Pommer, Ber. Dtsch. Chem. Ges. 54 (1921) 105.
[58] Chem. Fabrik von Heyden, Patent DE1159937, 1960. = Patent GB988773
[59] P. Cagniant, Bull. Soc. Chim. Fr. 1950, 29.
Thanks
(Chief Bee)
10-02-03 16:55
No 462283
roger2003: Read Post 461467 (Rhodium: "post numbers", General Discourse) then go back and edit your posts.
(Hive Bee)
11-19-03 23:42
No 471828
(Rated as: excellent)
Tetrahedron Letters 44 (2003) 1499-1501
A new, mild preparation of sulfonyl chlorides
Abstract: A new method was developed for the preparation of sulfonyl chlorides from sulfonic acids under neutral conditions using 2,4,6-trichloro-1,3,5-triazine as chlorinating agent.
Sulfonyl chlorides are important intermediates in organic synthesis, and are widely used for the preparation of amides(1) and esters(2). Generally, sulfonyl chlorides are prepared from the corresponding sulfonic acids by using thionyl chloride in dimethylformamide (DMF)(3). However, this process suffers from the tendency of the product to form a complex with DMF(4). Other methods include the reaction of sulfonic acids with phosphoryl chloride(5) or phosphorus pentachloride(6), both of which may require harsh conditions, such as heating at 170-180 C for many hours(7). In addition, there are disadvantages that these methods necessitate an excess of chlorinating reagent and that highly toxic and corrosive byproducts are formed.
Here we present a new method for the preparation of sulfonyl chlorides that involves treatment of sulfonic acids with 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride) in refluxing acetone under neutral conditions, a significantly milder procedure than those above. Cyanuric chloride is a commercially available, inexpensive reagent that has found increasing applications in organic synthesis. 2,4,6-trichloro-1,3,5-triazine and its derivatives have been used for the activation of carboxyl groups in the preparation of esters, amides, and peptides(8), alcohols and aldehydes(9), as well as alkyl chlorides(10) and acyl azides(11).
There is disagreement in the literature about the initial product of the reaction of carboxylic acids with cyanuric chloride. Some authors (8a,12) claim that the product is the acid chloride, whereas others (8d,9a,11,13) argue that acylated triazine is formed. We show here that in the case of sulfonic acids, the product is the acid chloride and not the acylated triazine. Furthermore, sulfonyl chlorides can be prepared in moderate to excellent yield by this reaction. The procedure consists of addition of 1 equiv. of cyanuric chloride to a mixture of 1 equiv. of dry sulfonic acid and 1 equiv. of triethylamine in dry acetone (scheme 1, method A) or addition of 1 equiv. of cyanuric chloride to 1 equiv of sodium sulfonate and catalytic amount of 18-crown-6 in dry acetone (Scheme 1, method B), followed by reflux for 20 h. After cooling, the solution is filtered through a Celite pad. The acetone is removed under vacuum and the sulfonyl chloride is purified either by distillation or column chromatography with silica gel merck 60 and an appropriate solvent system. The sulfonyl chlorides were identified by IR and H NMR data, and by comparison of melting or boiling points with those of authentic samples. The results are presented in table I.
A likely mechanism for this reaction is presented in scheme 2. Nucleophilic attack of the sulfonic acid anion on trichloro-s-triazine gives a delocalized carbanion, which yields the sulfonyl chloride and insoluble dichlorohydroxy-s-triazine.
In conclusion, we present a new, inexpensive and mild method for the preparation of sulfonyl chlorides, which employs cyanuric chloride and chlorinating agent.
Experimental
General procedure for synthesis of sulfonyl chlorides: Method A.
To 20 mmol of sulfonic acid and 20 mmol of triethylamine in 40 ml of acetone was added 20 mmol of cyanuric chloride and the mixture heated under reflux for 20 h. After cooling to room temperature the solution was filtered through a celite pad. Solvent was removed (rotary evaporator) and the sulfonyl chloride was purified by distillation or column chromatography.
Method B. To 20 mmol of sodium sulfonate and 1 mmol of 18-crown-6 ether in 40 ml acetone was added 20 mmol of cyanuric chloride and the procedure was followed as in method A.
Methods:
A:
R-SO2.OH + C3N3Cl3 ---> R-SO2.Cl + C3N3Cl2.OH
B:
R-SO2.ONa + C3N3Cl3 ---> R-SO2.Cl + C3N3Cl2.ONa
Mechanism:
R-SO2.OH + cyanuric acid + NEt3 ---->
R-SO2.O-C(Cl)(N3Cl2C2) + HN+Et3 ---->
R-SO2.Cl + N3Cl2C3.O- + HN+Et3
Prepared sulfonyl chlorides:
Yield:
R-SO3H Method CC Dist
----------------------------------
Me- A - 47%
Et- B - 74%
Me(CH2)3- B - 86%
Me(CH2)4- B - 70%
Benzene- A 90% 86%
B 94% -
p-Toluene- A 96% 94%
B 94% -
p-xylene- A 74% 70%
mesitylene- A 64% -
B 94% -
p-chlorobenzene A 76% -
B 96% -
p-acetaminobenz. A 66% -
B 70% -
B-napthalene A 88% -
B 89% -
refs on request, have fun guys.
(Chief Bee)
11-20-03 08:52
No 471909
Sounds a really good way of making the 2C-T-X precursor 2,5-dimethoxysulfonyl chloride without having to resort to the incredibly noxious compound chlorosulfonic acid (one of my personal enemies among chemicals, I really hate all compounds which upon contact with water breaks down to one or more noxious gases).
(Hive Addict)
11-20-03 15:40
No 471982
Does anyone want to share his favorite method of 2,4,6-trichloro-[1,3,5]-triazine production ?
--psyloxy--
(Hive Bee)
11-20-03 22:38
No 472061
this compound is very related to TCCA. You can buy it as "chlorine stabilizer"--just look for "cyanuric acid".
I am sure it can be bought in its chlorinated form, but if not, it could probably be chlorinated by your favorite method.
I believe cyanuric acid is made from urea, if you really wanted to make some.
Perhaps other compounds could be found which worked on the same principle.
It seems what is necesary is for a compound to have easy-leaving chlorine, and ability to absorb an -OH group.
Perhaps any unsaturated chloramine will do?
If you insisted further, maybe a wolf-kishner reduction on TCCA, or some similar foolishness?
That triethylamine bugs me, but I guess it's just there to eat protons.
I thought this paper wasn't exactly the best in terms of immediate applicability (Although cyanuric chloride is not very un-otc, umm, 18-crown-6 might be...), but rather it opened up a range of new possibilities. It's still up to us in the hive to make it work the best.
research...gotta love it
(Chief Bee)
11-20-03 23:13
No 472069
It isn't made, it is bought cheaply as an industrial chemical. You don't want to try even, as it is manufactured from hydrogen cyanide and chlorine gas at elevated temperatures: Post 382242 (Rhodium: "trichloroisocyanuric acid - cyanuric chloride", Novel Discourse)
(Hive Addict)
11-21-03 00:20
No 472084
(Rated as: good read)
(Although cyanuric chloride is not very un-otc, umm, 18-crown-6 might be...),
dear ning,
I highly doubt 18-crown-6 can be found in OTC sources (although I would very much like to be proved wrong). Crown ethers are generally quite expensive compounds (one catalog states 25 g/61.6 euro for 18-crown-6, the cheapest crown ether IIRC) although they are very interesting.
From "Phase transfer catalysts, properties and applications", E.V.Dehmlow and E.Weber, (Merck-Schuchardt), p 52:
In principle any chemical reaction where ions or ionic intermediates are involved in any form can be modified or improved through crown compounds. Among others, nucleophilic substitutions (e.g. halogen- and pseudohalogen substitutions, O-, N-, S-alkylations), reactions with carbanions, C-C bond formation (e.g. Darzen's, Knoevenagel condensations etc.), additions, eliminations, carbene generation, gas extrusions (N2, CO2), oxidations, reductions (dissolving metal, metal hydrides), rearrangements (Favorskii, Cope), isomerizations, and polymerisations are concerned. Further application fields of crown compounds are in the range of macrolide synthesis, of organo metal and protecting group reactions as well as phosphorous and silicon chemistry.
for further reading check the above publication, and also:
monographs
Phase transfer catalysts, principle and techniques, W.P. Weber & G.W.Gokel, New York, San Francisco, London 1978
Phase transfer catalysis, principles and techniques, C.M.Starks & C.Liotta, Concepts in Organic Chemistry 4, Springer-Verlag, Berlin, Heidelberg, New York 1977
Compendium of phase transfer reaction and related synthetic methods, W.E.Keller, Fluka AG, Buchs, Switzerland 1979
Phase transfer catalysis, monographs in modern chemistry 11, E.V.Dehmlow & S.S.Dehmlow, Verlag Chemie, Weinheim 1980 and 1983
Reviews
Crown ether chemistry: principles and applications, G.W.Gokel & H.D.Durst, Aldrichimica Acta 9, 3 (1976)
Principles and synthetic applications in crown ether chemistry, G.W.Gokel & H.D.Durst, Synthesis, 168 (1976)
Crown ethers, A.C.Knipe, J. Chem. Educ. 53, 618 (1976)
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(part I: general principles), J.Chem.Educ. 55, 350, (1978)
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Flight of the Bumble Bee (http://www.geocities.com/eric_vornoff/B
(Hive Addict)
11-21-03 19:56
No 472294
It isn't made, it is bought cheaply as an industrial chemical. You don't want to try even, as it is manufactured from hydrogen cyanide and chlorine gas at elevated temperatures
Exactly. You cannot make it. And most people cannot buy it. They're left out, their bodies shaking in the cold wind that blows along the snowy streets. Their hands stiff until the alcohol brings along some warm thoughts of better days - a summer they will never see.
Someday the source will be with me. Oh no - it was just another nip from the bottle of everclear.
--psyloxy--
"I'd rather be a small part of something great than a big part of a pile of shit" - Josh Homme
(Chief Bee)
11-21-03 20:15
No 472298
And most people cannot buy it.
Why not? If you cannot buy it locally, what prevents you from importing a smaller drum cheapish from an asian supplier? It's not like the suff is watched or anything...