EP1501772A1 - Procede de production de composes alcyne organiques - Google Patents

Procede de production de composes alcyne organiques

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Publication number
EP1501772A1
EP1501772A1 EP03718787A EP03718787A EP1501772A1 EP 1501772 A1 EP1501772 A1 EP 1501772A1 EP 03718787 A EP03718787 A EP 03718787A EP 03718787 A EP03718787 A EP 03718787A EP 1501772 A1 EP1501772 A1 EP 1501772A1
Authority
EP
European Patent Office
Prior art keywords
independently
group
radicals
formula
another
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03718787A
Other languages
German (de)
English (en)
Inventor
Robert Parker
Robert Reinhard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1501772A1 publication Critical patent/EP1501772A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/50—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed
    • C07C15/54—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed containing a group with formula

Definitions

  • the present invention relates to a process for the preparation of organic alkyne compounds of the formula I.
  • X and Y are the same or different organic radicals and shark is chlorine or bromine, in inert solvents under the action of microwave radiation, in the presence of at least one metal compound and at least one base.
  • aryl or alkenyl halides are reacted with terminal alkyne compounds under catalysis with palladium and copper salts at elevated temperature to give correspondingly substituted alkyne compounds.
  • a significant reduction in the reaction time can be achieved if the reaction is carried out under the influence of microwave radiation.
  • Inert solvents are understood to mean those liquids or liquid mixtures which, under the reaction conditions, do not react either with the starting materials or with the products.
  • inert solvents are polar, aprotic liquids, since when using protic liquids, undesired side reactions triggered by protonation must be expected.
  • solvent or “dissolve” etc. is also used in the following, even if, for example, the base (s) or metal compound (s) used is used in individual cases. are not completely dissolved, but are in suspension (or emulsion).
  • Suitable metal compounds are preferably those which are a metal selected from the group consisting of magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper , Silver, gold, zinc, cadmium and mercury. Copper compounds are particularly preferably used.
  • metal compounds are the halides, in particular the chlorides and bromides, but also the iodides, of the metals mentioned. If these halides form adducts with triarylphosphines, such as triphenylphosphine, they are used advantageously in the form of these adducts.
  • metal compounds in particular the metals already mentioned, should also be understood in elementary form as metal compounds.
  • combinations of several metal compounds, several metals, but also combinations of metals and metal compounds can be used.
  • the catalytically active metal-containing species in the reaction are not necessarily identical to the metal compounds used, but can only be formed in situ by reaction with the starting materials and / or the base (s).
  • Organic radicals X and Y are to be understood as meaning saturated or unsaturated hydrocarbon radicals and hydrocarbon radicals which contain both saturated and unsaturated parts of the molecule.
  • the hydrocarbon radicals can also contain conventional heteroatoms, such as nitrogen, oxygen, phosphorus, sulfur, fluorine, chlorine, bromine or else iodine.
  • the organic radicals X and Y usually have molar masses of up to about 600 g / mol. In individual cases, however, the molecular weights of the radicals X and Y can also be higher.
  • Preferred organic radicals X and Y contain saturated or unsaturated carbo- or heterocyclic radicals in which both -Hai, i.e. Chlorine or bromine, as well as H-C ⁇ C- are bound directly to the saturated or unsaturated carbo- or heterocyclic radicals.
  • X corresponds to a remainder of the formula Ha pl_ ⁇ l_ ( A l_ ⁇ 3 ) m , _ ( T l_ B l_ ) m _ T 3_ (IIa) and Y is a radical of the formula Ilb
  • P 1 , P 2 independently of one another are hydrogen, C 1 -C 2 -alkyl, a polymerizable group or a group suitable for polymerization, or a radical which bears a polymerizable or suitable group for polymerization,
  • P 1 and / or P 2 each correspond to a radical P 1 'and / or P 2 ', which denotes a precursor group which is stable under the reaction conditions and which corresponds to the corresponding polymerizable or suitable groups P 1 and / or P 2 or the radicals P 1 and / or P 2 , which carry a polymerizable or suitable group for polymerization, can be reacted,
  • Y 1 , Y 2 , Y 3 , Y 4 independently of one another are a single chemical bond, -0-, -S-, -CO-, -C0-0-, -0-C0-, -CO-N (R) -, - (R) N-CO-, -0-CO-O-, -O-CO-N (R) -, - (R) N-CO-O- or - (R) N-CO-N (R ) -,
  • B 1 , B 2 independently of one another are a chemical single bond
  • R independently of one another and independently of the respective meaning in Y 1 to Y 4 , B 1 and B 2 are hydrogen or C 1 -C 4 -alkyl,
  • a 1 , A 2 independently of one another spacers having one to 30 carbon atoms,
  • T 1 , T 2 , T 3 , T 4 independently of one another divalent saturated or unsaturated carbo- or heterocyclic radicals and
  • n are independently 0 or 1.
  • radicals T 1 to T 4 in the formulas Ila and Ilb are in particular those selected from the group consisting of and
  • P 1 and P 2 in formula I are to be mentioned as -C-Ci 2 ⁇ Al yl branched or unbranched C -C- 2 alkyl chains, for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl , 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl , 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2nd , 3-dimethylbutyl, 3, 3-dimethylbutyl
  • Preferred alkyl for P 1 and P 2 are the branched or unbranched Ci-C ⁇ -alkyl chains, such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl , n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl and n-hexyl.
  • P 1 and P 2 are particularly suitable:
  • radicals R 1 to R 3 can be the same or different and are hydrogen or C 1 -C 4 - Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
  • Spacers A 1 and A 2 are all groups known to the person skilled in the art for this purpose.
  • the spacers generally contain one to 30, preferably one to 12, particularly preferably one to six carbon atoms and consist of predominantly linear aliphatic groups. They can be interrupted in the chain, for example by non-adjacent oxygen or sulfur atoms or imino or alkylimino groups, such as methylimino groups. Fluorine, chlorine, bromine, cyano, methyl and ethyl are suitable as substituents for the spacer chain.
  • spacers are for example:
  • u, v and w take integer values and u stands for 1 to 30, preferably 1 to 12, v for 1 to 14, preferably 1 to 5, and w for 1 to 9, preferably 1 to 3.
  • Preferred spacers are ethylene, propylene, n-butylene, n-pentylene and n-hexylene.
  • the radicals T 1 to T 4 are ring systems which are formed by fluorine, chlorine, bromine, cyano, hydroxyl, formyl, nitro, C 1 -C 2 -alkyl, C 1 -C 2 o-alkoxy, C 1 -C 20 -Alkoxycarbonyl, C ! -C 20 mono-alkylaminocarbonyl, -C-C o-alkylcarbonyl, -C-C 2 o-alkylcarbonyloxy or -C-C 2 Q-alkylcarbonylamino may be substituted.
  • Preferred radicals T 1 to T 4 are:
  • radicals P 1 'and / or P 2 ' denote stable precursor groups under the reaction conditions, the latter then being able to be converted or substituted by the corresponding reactive radicals P 1 and / or P 2 in a subsequent step.
  • P 1 '-Y 1 - (A 1 -Y) m' - (T 1 -B 1 -) m -T -C ⁇ CT 4 - (B 2 -T -) n - (Y 4 -A) n - -Y 2 -P 2 ' correspond to be regarded as direct products of the rapid manufacturing process according to the invention.
  • pl hydrogen
  • Y 1 -0-
  • m ' 0,
  • both hydroxyl and carboxyl groups can also be present.
  • the starting materials of the formulas Ia and Ib are usually dissolved in a 2: 1 to 1: 2 molar ratio together with the at least one metal compound and the at least one base in the inert solvent.
  • the solution is normally prepared at room temperature, but in individual cases can also take place at a temperature above or below.
  • the temperature during the actual implementation under the influence of microwave radiation is not critical.
  • the reaction usually takes place at temperatures between room temperature and the boiling point of the solvent used.
  • DMF Dimethylformamide
  • NMP N-methylpyrrolidone
  • a mixture of the two is preferably used as the solvent.
  • DMF is particularly preferably used as solvent (or as suspending agent) in the process according to the invention.
  • a compound selected from the group consisting of alkali metal carbonates, alkali metal phosphates and tri (C 1 -C 4 -alkyl) amines is preferred as at least one base, the alkali metal carbonates being emphasized.
  • the group of suitable bases includes in particular sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, trimethyl, triethyl and triisopropylamine.
  • Potassium carbonate is particularly preferably used.
  • potassium iodide can also be advantageous for the reaction. Whether such a positive effect can be seen and in what amounts the potassium iodide may be present must be added can easily be determined by preliminary tests.
  • the power of the microwave radiation source used is usually a few tens to a few hundred watts and must be adapted to the volume of the reaction mixture.
  • the suitable dimensioning of the radiation source is usually known to the person skilled in the art and / or can easily be determined by preliminary tests.
  • the alkyne compounds obtained are worked up and purified by customary methods of organic synthesis.
  • the solid essentially potassium carbonate
  • dichloromethane was filtered off, washed with 100 ml of dichloromethane and the solution obtained was extracted three times with 50 ml each of a saturated, aqueous sodium chloride solution.
  • the dichloromethane solution was dried over sodium sulfate and the solvent was then removed on a rotary evaporator.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procédé de production de composés alcyne organiques de formule X-C=C-Y par mise en réaction de composés halogènes organiques de formule X-Hal avec des composés alcyne terminaux organiques de formule H-C=C-Y, X et Y représentant des restes organiques identiques ou différents et Hal représentant chlore ou brome, dans des solvants inertes sous l'effet du rayonnement de micro-ondes, en présence d'au moins un composé métallique et d'une base.
EP03718787A 2002-04-29 2003-04-25 Procede de production de composes alcyne organiques Withdrawn EP1501772A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10219201A DE10219201A1 (de) 2002-04-29 2002-04-29 Verfahren zur Herstellung von organischen Alkinverbindungen
DE10219201 2002-04-29
PCT/EP2003/004288 WO2003093201A1 (fr) 2002-04-29 2003-04-25 Procede de production de composes alcyne organiques

Publications (1)

Publication Number Publication Date
EP1501772A1 true EP1501772A1 (fr) 2005-02-02

Family

ID=28798918

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03718787A Withdrawn EP1501772A1 (fr) 2002-04-29 2003-04-25 Procede de production de composes alcyne organiques

Country Status (9)

Country Link
US (1) US20050178650A1 (fr)
EP (1) EP1501772A1 (fr)
JP (1) JP2005532307A (fr)
KR (1) KR20050006197A (fr)
CN (1) CN1330613C (fr)
AU (1) AU2003222836A1 (fr)
DE (1) DE10219201A1 (fr)
TW (1) TW200306965A (fr)
WO (1) WO2003093201A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0618832D0 (en) * 2006-09-25 2006-11-01 Phoenix Chemicals Ltd Chemical process
KR101054267B1 (ko) * 2009-03-19 2011-08-08 강원대학교산학협력단 아세틸렌 유도체의 제조 방법
US9008884B2 (en) 2010-12-15 2015-04-14 Symbotic Llc Bot position sensing
CN107501036B (zh) * 2017-09-15 2020-03-17 安徽省科学技术研究院 一种苯乙炔基碘类化合物的合成方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4871868A (en) * 1987-03-11 1989-10-03 Takeda Chemical Industries, Ltd. Production of substituted acetylenic compounds
SE509731C2 (sv) * 1996-05-14 1999-03-01 Labwell Ab Metod för palladium-katalyserade organiska reaktioner innefattande ett uppvärmningssteg utfört med mikrovågsenergi

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03093201A1 *

Also Published As

Publication number Publication date
AU2003222836A1 (en) 2003-11-17
TW200306965A (en) 2003-12-01
JP2005532307A (ja) 2005-10-27
WO2003093201A1 (fr) 2003-11-13
KR20050006197A (ko) 2005-01-15
DE10219201A1 (de) 2003-11-06
CN1330613C (zh) 2007-08-08
CN1649806A (zh) 2005-08-03
US20050178650A1 (en) 2005-08-18

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