WO2007022901A1 - Elaboration de thioalkylamines au moyen d'acide chlorosulfonique - Google Patents

Elaboration de thioalkylamines au moyen d'acide chlorosulfonique Download PDF

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Publication number
WO2007022901A1
WO2007022901A1 PCT/EP2006/008061 EP2006008061W WO2007022901A1 WO 2007022901 A1 WO2007022901 A1 WO 2007022901A1 EP 2006008061 W EP2006008061 W EP 2006008061W WO 2007022901 A1 WO2007022901 A1 WO 2007022901A1
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WIPO (PCT)
Prior art keywords
alkyl
halo
different
alkoxy
group
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PCT/EP2006/008061
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English (en)
Inventor
Harry Blaschke
Sergiy Pazenok
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Bayer Cropscience Ag
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Priority to BRPI0615132-9A priority Critical patent/BRPI0615132A2/pt
Priority to MX2008002437A priority patent/MX2008002437A/es
Priority to EP06776867A priority patent/EP1981841A1/fr
Publication of WO2007022901A1 publication Critical patent/WO2007022901A1/fr
Priority to IL189465A priority patent/IL189465A0/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated

Definitions

  • the present invention relates to a novel process for the preparation of known thioalkylamine derivatives.
  • a first method for the preparation of thiols is based on the hydrolytic cleavage of thiazoline or thiazolidinone derivatives (cf. e.g. J. Med. Chem. 1965. 8, 762; JP 59-231064, Bull. Soc. Chim. Fr. 1967, 3637).
  • thiazoline or thiazolidinone derivatives have to be prepared first via several reaction steps the overall yield of this method is very low.
  • reaction of oxazoline- or oxazolidinone derivatives with thiols is a method for the preparation of sulfides (cf. e.g. J. Org. Chem. 1992. 57, 6257; J. Med. Chem. 1984. 27. 1354).
  • a hydrolytic process is required to obtain reaction products as amides according to this method.
  • no reaction is observed, if the oxazolidine ring of the starting compounds is e.g. alkyl substituted.
  • aromatic sulfides can be prepared using this method because of the acidity of the mercaptans.
  • the hydrolytic cleavage of amides which can be obtained by reaction of amino alcohols with mercaptans in the presence of carboxylic acids, also furnishes sulfides (cf. e.g. DE-OS 14 93 534).
  • This method has to be carried out at high temperature and under pressure using long reaction times and is therefore restricted to the synthesis of sulfides. Additionally a hydrolytic step is required to obtain the reaction products from amides.
  • a method for the conversion of thioalkylalcohols into thioalkylamines is represented by the Ritter reaction with subsequent hydrolytic cleavage (cf. e.g. DE-OS 20 45 905). This method employs - -
  • a further method for the preparation of thioalkylamine derivatives uses as starting material amino alcohols which are reacted with sulfuric acid to give the corresponding esters in a first step (cf. WO 01/23350). After evaporation to dryness this esters are further converted by reaction with mercaptans. The required evaporation after the first reaction step causes problems when this process is employed to a large scale production.
  • R 1 and R 2 in each case independently of one another represent hydrogen, Ci-C 4 -alkyl, C 3 -Cg- cycloalkyl, C 3 -C 8 -cycloalkyl-C ⁇ -C 4 -alkyI, hydroxy-C
  • R 3 and R 4 independently of one another represent hydrogen or Ci-C 4 -alkyl
  • R 5 and R 6 independently of one another represent hydrogen, Ci-C 4 -alkyl, unsubstituted or mono- to pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of halogen, cyano, nitro, C]-C 4 -alkyl, C 3 -Cg-cycloalkyl, Q-C 4 - alkoxy, C,-C 4 -alkylthio, C,-C 4 -alkylsulfinyl, C,-C 4 -alkylsulfonyl, halo-C,-C 4 -alkyl, halo-
  • R represents unsubstituted or mono- or polysubstituted Ci-Ci 2 -alkyl, where the substituents are identical or different and are selected from the group consisting of halogen, hydroxy,
  • n 1, 2, 3, 4, 5, 6, 7 or 8, where the group C(R')R 2 may be identical or different, when n is greater than 1,
  • R 1 and R 2 furthermore together represent C 2 -C 5 -alkyIene, R 1 furthermore represents together with R 3 or R 5 C 3 -C 5 -alkylene,
  • R 3 and R 4 furthermore together represent C 4 -C 6 -alkylene
  • R 3 and R 5 furthermore together represent C 2 -Gralkylene
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and n have the above given meanings
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and n have the above given meanings
  • M represents hydrogen, ammonium or an alkali metal atom
  • the thioalkylamines of the formula (I) can be obtained in a simple manner in a very good space-time yield.
  • the reaction according to the invention therefore has the advantage of an increased reaction rate. This leads to the technical advantage of a high space-time yield.
  • the process according to the invention has the further advantage that the solution of the intermediates of formula (III) need not to be evaporated to dryness.
  • the reaction mixture can be stirred at any time of the process which decreases the risk of a breaking reaction vessel in industrial plants.
  • the formula (II) provides a general definition of the amino alcohols required as starting materials for carrying out the first step of the process according to the invention.
  • Preferred as starting material are amino alcohols of the formula (II), in which
  • R 1 and R 2 in each case independently of one another represent hydrogen, C
  • R 3 and R 4 independently of one another represent hydrogen or Ci-C 4 -alkyl
  • R 5 and R 6 independently of one another represent hydrogen, C r C 4 -alkyl, unsubstituted or mono- to pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, Ci-Q-alkyl, C 3 -C 6 -cycloalkyl, C
  • n 1, 2, 3, 4, 5 or 6, where the group C(R ] )R 2 may be identical or different, when n is greater than 1,
  • R 1 furthermore represents together with R 3 or R 5 C 3 -C 5 -alkylene
  • R 3 and R 4 furthermore together represent C 4 -C 6 -alkylene
  • R 3 and R 5 furthermore together represent C 2 -C 4 -alkyIene
  • R 5 and R 6 furthermore together represent C 4 -C 6 -alkylene.
  • Particularlv preferred as starting material are amino alcohols of the formula (II), in which
  • R 1 and R 2 in each case independently of one another represent hydrogen, methyl, ethyl, n-, i-pro- pyl, n-, i-, S-, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl, cyclobutyl- ethyl, cyclopentylethyl, cyclohexylethyl, hydroxymethyl, hydroxyethyl; unsubstituted or mono- to trisubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-, i-propyl,
  • R 3 and R 4 independently of one another represent hydrogen, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl,
  • R 5 and R 6 independently of one another represent hydrogen, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, unsubstituted or mono- to trisubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, methylthio, ethylthio, n-, i-propylthio, n-, i-, s-
  • n 1, 2, 3, 4, 5 or 6, where the group C(R*)R 2 may be identical or different, when n is greater than 1 ,
  • R 1 and R 2 furthermore together represent -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ),,-, -(CH 2 ) 5 -,
  • R 1 furthermore represents together with R 3 or R 5 -(CH 2 ) 3 -, -(CH 2 ) 4 -, -(CH 2 ) 5 -,
  • R 3 and R 4 furthermore together represent -(CH 2 ) 4 -, -(CH 2 ) 5 -, -(CH 2 ) 6 -,
  • R 3 and R 5 furthermore together represent -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -,
  • R 5 and R 6 furthermore together represent -(CH 2 ) 4 -, -(CH 2 ) 5 -, -(CH 2 ) 6 -.
  • R 1 and R 2 in each case independently of one another represent hydrogen, methyl, ethyl, n-, i-pro- pyl, n-, i-, s-, t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, hydroxymethyl, hydroxyethyl; unsubstituted or mono- to trisubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclopenty!, cyclohexyl, methoxy, ethoxy, n-, i-prop
  • R 3 and R 4 independently of one another represent hydrogen, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl,
  • n 1, 2, 3 or 4, where the group C(R')R 2 may be identical or different, when n is greater than 1 ,
  • R 1 and R 2 furthermore together represent -(CH 2 ) r , -(CH 2 ) 3 -, -(CH 2 ) 4 -, -(CH 2 ) 5 -,
  • R 1 furthermore represents together with R 3 or R 5 -(CH 2 V, -(CH 2 J 4 -, -(CH 2 ) 5 -,
  • R 3 and R 4 furthermore together represent -(CH 2 ) 4 -, -(CH 2 ) 5 -, -(CH 2 ) 6 -,
  • R 3 and R 5 furthermore together represent -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ),,-,
  • R 5 and R 6 furthermore together represent -(CH 2 ) 4 -, -(CH 2 ) 5 -, -(CH 2 ) 6 -.
  • amino alcohols of the formula (IT) in which R 1 and R 2 in each case independently of one another represent hydrogen, methyl, ethyl, n-, i-pro- pyl, n-, i-, s-, t-butyl,
  • R 3 and R 4 independently of one another represent hydrogen, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl,
  • R 5 and R 6 independently of one another represent hydrogen, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl,
  • n 1 or 2
  • the group C(R')R 2 may be identical or different, when n is greater than 1.
  • Amino alcohols of the formula (II) are widely known and/or can be prepared according to known methods.
  • the formula (FV) provides a general definition of the mercaptans or salts thereof required as starting materials for carrying out the second step of the process according to the invention.
  • Preferred as starting material are mercaptans or salts thereof of the formula (FV), in which
  • R represents unsubstituted or mono- or polysubstituted Ci-Ci 2 -alkyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxy, Ci-G
  • M represents hydrogen, ammonium or an alkali metal atom (preferably sodium, potassium, lithium and caesium).
  • Particularly preferred as starting material are mercaptans or salts thereof of the formula (FV), in which
  • R represents in each case unsubstituted or mono- or polysubstituted methyl, ethyl, n-, i-pro- pyl, n-, i-, s-, t-butyl, in each case the isomeric pentyls, hexyl, octyl, decyls and dodecyls, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxy, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, trifluoromethoxy, trichloromethoxy, difluoromethoxy, dichloromethoxy, di- fluorochloromethoxy, fluorodichloromethoxy, methylthio, ethylthio, n-, i-propylthio, n-, i
  • M represents hydrogen, ammonium, sodium, potassium, lithium and caesium.
  • R represents in each case unsubstituted or mono- or polysubstituted methyl, ethyl, n-, i-propyl, n-, i-, S-, t-butyl, in each case the isomeric pentyls, hexyl, octyl, decyls and dodecyls, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxy, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, trifluoromethoxy, trichloromethoxy, methylthio, ethylthio, n-, i-propylthio, t-butylthio, methylsulfinyl, ethylsulfinyl, n-, i-propylsul
  • M represents hydrogen, ammonium, sodium and potassium.
  • R represents in each case unsubstituted or mono- or polysubstituted methyl, ethyl, n-, i-propyl or n-, i-, S-, t-butyl where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxy, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, trifluoromethoxy, trichloromethoxy, methylthio, ethylthio, n-, i-propylthio, t-butylthio, methylsulfinyl, ethylsulfinyl, n-, i-propylsulfinyl, t-butylsulfinyl, methylsulfonyl, ethylsulfonyl,
  • M represents sodium or potassium.
  • Mercaptans or salts thereof of the formula (FV) are widely known and/or can be prepared according to known methods.
  • Saturated or unsaturated hydrocarbon radicals e.g. alkyl and alkenyl
  • halogen e.g. haloalkyl
  • Radicals subsituted by halogen are mono- or polysubsituted up to perhalogenation.
  • the halogen atoms may be identical or different.
  • Halogen represents fluorine, chlorine, bromine or iodine.
  • the first step of the reaction according to the invention can be carried out by addition of the chlorosulfonic acid into the amino alcohols of the formula (II). This procedure is preferably carried out with mechanical stirring.
  • the addition of the chlorosulfonic acid into the amino alcohol of the formula (II) is preferably done with cooling to keep the temperature below 70 0 C, while a temperature range between 30 and 50 0 C is particularly preferred. In general a carbonization will not be observed even if higher substituted amino alcohols are employed.
  • the amino alcohols are applied in liquid form or as a solution in inert organic solvent.
  • the first step of the reaction is expediently carried out under atmospheric pressure, although it is also possible to work under reduced or elevated pressure. Particular preference is given to carrying out the reaction under atmospheric pressure.
  • the reaction time can be different depending on the scale of the reaction and may vary between 10 min and 4 hours.
  • the first step of the process is carried out by reacting 0.5 to 2, preferably 0.8 to 1.2, particularly preferably 0.9 to 1.1 moles of amino alcohol per mole of chlorosulfonic acid.
  • the first step of the process is carried out in practice by reacting, for example, 1 mol of an amino alcohol of formula (II) with 1 mol of HSO 3 CI in organic solvent.
  • the sulfuric acid esters of the formula (III) may be isolated. Preferably these esters of formula (III) are used without isolation for the conversion in the second step of the process according to the invention.
  • the second step of the reaction according to the invention can be carried out by addition of the sulfuric acid esters of the formula (HI) into the mercaptans or salts thereof of formula (FV).
  • the addition of the sulfuric acid esters of the formula (111) into the mercaptan or salts thereof of formula (IV) is done within between 10 min up to 2 h, depending on the scale of the reaction, preferably within between 20 min and 2 h, particularly preferably within between 30 min and 1 h.
  • the second step of the reaction according to the invention can be carried out by addition of the sulfuric acid esters of formula (III) as a solution or solid into mercaptans or their salts of formula (FV) preferably in water.
  • the pH of the reaction mixture has to be kept in the range of 10-12 while adding the ester.
  • the base as a solid is added directly to the mercaptide or its salt in water, followed by addition of the sulfonate as a solid or concentrated solution.
  • the addition of the sulfonate to the mixture of mercaptide and NaOH allows to increase the yield up to 92-95% (vers. EP 1231698 yield 82 %).
  • the second step of the process is carried out in the presence of a base.
  • a base examples which may be mentioned are: alkali metal and alkaline earth metal hydroxides, such as NaOH, KOH, Ca(OH)2, alkali metal carbonates or hydrogencarbonates, such as Na2CO3, I ⁇ 2 CO 3 , K2CO3, CS2CO3 or NaHC ⁇ 3 and KHCO3.
  • alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH)2
  • alkali metal carbonates or hydrogencarbonates such as Na2CO3, I ⁇ 2 CO 3 , K2CO3, CS2CO3 or NaHC ⁇ 3 and KHCO3.
  • reaction temperatures employed to the second step of the reaction according to the invention may be varied over a broad range.
  • the reaction is carried out between 30 0 C and 150 0 C, preferably between 50 0 C and 120 0 C, particularly preferably between 7O 0 C and 100 0 C.
  • the second step of the reaction is expediently carried out under atmospheric pressure, although it is also possible to work under reduced or elevated pressure. Particular preference is given to carrying out the reaction under atmospheric pressure.
  • the second step of the reaction according to the invention may be carried out in the presence of a further diluent, where all customary inert organic solvents apply.
  • a further diluent such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decaline; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichlorethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl tert.-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1,2-diethoxyethane or anisole;
  • the second step of the process is carried out in practice by reacting, for example, 1 mol of a sulfuric acid ester of formula (III) with between 1 and 10 mol, preferably between 1 and 5 mol, particularly preferably between 1 and 1.5 mol of a mercaptan or salt thereof of formula (FV) in the presence of a base, to keep the pH value in general between pH 1 1 and 12.
  • the reaction time can be reduced by using Phase transfer catalysts (PTC) like Tetralkylammonium, Tetraalkyl-, Tetraarylphosphonium, Guanidinium or pyridinuim salts.
  • PTC Phase transfer catalysts
  • Prefered catalysts are tetramethylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium bromide, tetraphenylphosphonium bromide and 18-crown-6.
  • the end-product can be isolated using standard procedures, e.g. cristallization, chromatography, extraction and distillation.
  • the mixture is cooled to 32 0 C and all the following procedures are performed at this temperature.
  • 100 ml methyl tert.-butyl ether is added, the mixture is stirred and the organic layer is separated.
  • the aqueous layer is extracted with two 100 ml portions of tert.-butyl ether.
  • the combined organic layers were dried over anhydrous sodium sulfate. After filtration the solvent was removed at 2O 0 C and under 150 mbar reduced pressure.

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

Abstract

La présente invention concerne un procédé permettant l'élaboration de composés représentés par la formule (I). Dans un premier temps, on prend des alcools aminés représentés par la formule (II), et on les fait réagir avec de l'acide chlorosulfonique, ce qui donne les esters d'acide sulfurique représentés par la formule générale (III). Dans un deuxième temps, on fait réagit ces esters avec des mercaptans ou sels de mercaptans dont le formule est 'RSM' (formule IV), en présence d'un diluant et d'une base. Dans ces formules, R1, R2, R3, R4, R5, R6, R, n et M sont tels que spécifiés dans la description.
PCT/EP2006/008061 2005-08-24 2006-08-16 Elaboration de thioalkylamines au moyen d'acide chlorosulfonique WO2007022901A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BRPI0615132-9A BRPI0615132A2 (pt) 2005-08-24 2006-08-16 preparação de tioalquilaminas empregando-se ácido clorossulfÈnico
MX2008002437A MX2008002437A (es) 2005-08-24 2006-08-16 Preparacion de tioalquilaminas usando acido clorosulfonico.
EP06776867A EP1981841A1 (fr) 2005-08-24 2006-08-16 Elaboration de thioalkylamines au moyen d'acide chlorosulfonique
IL189465A IL189465A0 (en) 2005-08-24 2008-02-12 Preparation of thioalkylamines using chlorosulfonic acid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP05018348 2005-08-24
EP05018348.2 2005-08-24

Publications (1)

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WO2007022901A1 true WO2007022901A1 (fr) 2007-03-01

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PCT/EP2006/008061 WO2007022901A1 (fr) 2005-08-24 2006-08-16 Elaboration de thioalkylamines au moyen d'acide chlorosulfonique

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EP (1) EP1981841A1 (fr)
KR (1) KR20080036634A (fr)
BR (1) BRPI0615132A2 (fr)
IL (1) IL189465A0 (fr)
MX (1) MX2008002437A (fr)
TW (1) TW200722409A (fr)
WO (1) WO2007022901A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9145354B2 (en) 2011-11-01 2015-09-29 Astex Therapeutics Limited Pharmaceutical compounds

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001023350A1 (fr) * 1999-09-28 2001-04-05 Nihon Nohyaku Co., Ltd. Derives de thioalkylamine et methode de preparation desdits derives
WO2003099777A1 (fr) * 2002-05-24 2003-12-04 Bayer Cropscience Ag Procede de preparation de derives de thioalkylamine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001023350A1 (fr) * 1999-09-28 2001-04-05 Nihon Nohyaku Co., Ltd. Derives de thioalkylamine et methode de preparation desdits derives
EP1216988A1 (fr) * 1999-09-28 2002-06-26 Nihon Nohyaku Co., Ltd. Derives de thioalkylamine et methode de preparation desdits derives
WO2003099777A1 (fr) * 2002-05-24 2003-12-04 Bayer Cropscience Ag Procede de preparation de derives de thioalkylamine

Non-Patent Citations (3)

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Title
P.M.R. BARKWORTH, ET AL.: "Compounds with bridgehead nitrogen. Part 43. The reaction between trans-e-aminocycloalkanethiols and formaldehyde", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1, no. 11, November 1982 (1982-11-01), ROYAL SOCIETY OF CHEMISTRY, LETCHWORTH, GB, pages 2777 - 2281, XP002404071 *
V. SATTA, ET AL.: "Sulphatoalkyl amines", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 75, no. 16, 20 August 1953 (1953-08-20), AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, pages 4101 - 4102, XP002404101 *
Y. INOUE, ET AL.: "Synthesis and spectral properties of N-sulphated and/or O-sulphated amino alcohols", JOURNAL OF ORGANIC CHEMISTRY, vol. 38, no. 10, 18 May 1973 (1973-05-18), AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, pages 1810 - 1813, XP002404070 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9145354B2 (en) 2011-11-01 2015-09-29 Astex Therapeutics Limited Pharmaceutical compounds

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KR20080036634A (ko) 2008-04-28
BRPI0615132A2 (pt) 2011-05-03
IL189465A0 (en) 2008-08-07
MX2008002437A (es) 2008-04-03
TW200722409A (en) 2007-06-16
EP1981841A1 (fr) 2008-10-22

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