US20030114721A1 - Method for functionalising a double bond - Google Patents

Method for functionalising a double bond Download PDF

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Publication number
US20030114721A1
US20030114721A1 US10/203,075 US20307502A US2003114721A1 US 20030114721 A1 US20030114721 A1 US 20030114721A1 US 20307502 A US20307502 A US 20307502A US 2003114721 A1 US2003114721 A1 US 2003114721A1
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Prior art keywords
advantageously
formula
radicals
chosen
carbon
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US10/203,075
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English (en)
Inventor
Nicolas Roques
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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Assigned to RHODIA CHIMIE reassignment RHODIA CHIMIE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROQUES, NICOLAS
Publication of US20030114721A1 publication Critical patent/US20030114721A1/en
Priority to US10/740,802 priority Critical patent/US20040147789A1/en
Priority to US10/866,586 priority patent/US7230147B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • 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
    • C07B37/02—Addition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/34—Halogenated alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton

Definitions

  • the present invention relates to a process for functionalizing a double bond, and more particularly a double bond bearing a metalloid atom. More particularly, the present invention is directed toward adding to a double bond, on the one hand, and to one of the atoms a halogen atom and, on the other hand, to the other carbon-based radical whose carbon atom is perhalogenated.
  • bromide is difficult and expensive to handle, especially on account of the high instability of this bromide.
  • the bromide like the chloride, is a powerful oxidizing agent which can modify the capacities for survival of the products obtained during this addition.
  • the bromide ions formed during the reaction that react with the residual bromide can lead to bromine, which is then a source of further spurious reactions.
  • Trifluoromethanesulfonyl chloride which is occasionally known as triflyl chloride, is significantly less reactive than the bromide; thus, it has been attempted to use very specific ruthenium complexes (Ru(P ⁇ 3 )Cl 2 ) to catalyze the addition to double bonds.
  • one of the aims of the present invention is to define a family of compounds bearing already-functionalized double bonds, that can give acceptable addition yields with a technique of decomposition of sulfonyl chloride initiated by free radicals.
  • Another aim of the present invention is to provide an optimization of the operating conditions for this novel family of compounds.
  • Another aim of the present invention is to provide a process that does not require expensive catalysts such as those based on metals from column VIII, especially of the platinum mine, and in particular ruthenium.
  • Another aim of the present invention is to provide a process in which ruthenium, especially in the form coordinated with phosphines and especially aromatic phosphines, is present in an amount such that the [Ru]/[sulfonyl chloride perhalogenated on the sulfur-bearing carbon] molar ratio is not more than 1 ⁇ , advantageously 0.1 ⁇ and preferably 0.01 ⁇ . It is even preferable for it not to be present.
  • Another aim of the present invention is to provide a process in which the platinum mine metals are present in an amount such that the [sum of the platinum mine metals]/[sulfonyl chloride perhalogenated on the sulfur-bearing carbon] molar ratio is not more than 1 ⁇ , advantageously 0.1 ⁇ and preferably 0.01 ⁇ . It is even preferable that they are not present.
  • Another aim of the present invention is to provide a process in which the metals from column VIII are present in an amount such that the [sum of the metals from column VIII]/[sulfonyl chloride perhalogenated on the sulfur-bearing carbon] molar ratio is not more than 1 ⁇ , advantageously 0.16 and preferably 0.0 ⁇ . It is even preferable for them not to be present.
  • Another aim of the present invention is to provide novel intermediates allowing novel synthetic routes.
  • R 1 , R 2 and R 3 which may be identical or different, are chosen from hydrogen and hydrocarbyls attached to said double bond via a carbon of Sp 3 hybridization;
  • halogens advantageously chlorine and fluorine
  • Y is a chalcogen, advantageously a light chalcogen
  • q is zero or an integer not more than 3, advantageously not more than 2 and preferably not more than 1, with the condition that when Y is oxygen, q is equal to zero;
  • R′ represents a hydrocarbyl, advantageously of not more than four carbons, or preferably a hydrogen
  • m is equal to 1 or preferably to zero;
  • R 4 is chosen from a hydrocarbyl or silyl group
  • perhalogenated carbon should be understood as meaning a carbon of sp 3 nature optionally substituted with not more than two, and advantageously not more than one, electron-withdrawing group(s), and bearing no hydrogen, all the other atoms being halogens. It is preferable for these halogens borne by said perhalogenated carbon all to be chlorine or fluorine and preferably all fluorine.
  • radicals R 1 , R 3 and R 2 when they are hydrocarbyls (i.e. comprising hydrogen and carbon, but possibly comprising other atoms), are attached to the double bond via one of their sp 3 carbons, otherwise the reactivity toward the sulfonyl chloride is greatly affected thereby.
  • the presence of an aromatic directly attached to the double bond plays an extremely unfavorable role. It is also recommended to avoid carbon atoms that are both allylic and benzylic. More generally, even when they are not conjugated with said double bond, the presence of an aromatic in the molecule is unfavorable.
  • the presence of an aromatic in Z is unfavorable especially when an aromatic nucleus is separated from a carbon of said double bond by less than two atoms of sp 3 hybridization (oxygen or carbon, preferably at least two sp 3 carbons).
  • Z Z ⁇ (CHR′) m —Y(O) q —R 4 and that which indicates that Z is such that ZH is an oxygenated acid, especially when m is equal to zero, when q is equal to zero, when Y is oxygen and R 4 is a hydrocarbon radical attached to Y via an electron-withdrawing function such as, especially, carbonyl (—CO—), carbonate (—CO—O—), sulfonyl (SO 2 ), sulfoxide (—SO—), sulfate (—SO 3 —), phosphate [P( ⁇ O)(—O—)O—], phosphonate [P( ⁇ O)(—O—)—] and phosphinate [P( ⁇ O)(—)—].
  • radicals R 1 , R 3 and R 2 such that at least one and preferably two of these three radicals is hydrogen. It is also preferable that neither R 1 nor R 2 is tertiary. It is also preferable that at least one, and even both, of the radicals R 1 and R 2 are hydrogen.
  • the initiator generating the free radicals releases these radicals after a homolytic cleavage, i.e. a cleavage taking place between two atoms of the same element and generating an electron radical on each of the two atoms.
  • This cleavage may be actinic, catalytic or, preferably, thermal.
  • the cleavage may also be heterolytic when systems are used involving metals that have two valency states (iron or copper) with peroxides and especially hydroperoxides.
  • Examples of preferred initiators that should be mentioned include various peroxides, preferably symmetrical, and various azo compounds, such as azobisisobutyronitrile (reference may be made especially to the “Polymer Handbook”).
  • peroxides mention may be made of alkyl peroxides and especially tert-alkyl peroxides, and acyl peroxides, especially alkanoyl peroxides, that are preferably symmetrical.
  • acyl peroxides that may be used are preferably peroxides whose acyls are of low molecular weight, i.e. their carbon number is not more than 10, and preferably not more than 6 when they are aliphatic, but it is preferable to use acyl peroxides of aromatic nature, for instance benzoyl peroxide.
  • the free-radical initiator is advantageously not more than 0.2 times the molar amount of the sulfonyl chloride, preferably not more than 0.1 times, the optimum zone being between 1% and 8% of the amount of sulfonyl chloride.
  • the reaction is advantageously conducted such that the release of the free radicals takes place gradually.
  • a good technique for achieving this objective consists in adding the initiator, i.e. the free-radical generator, slowly and gradually.
  • Another technique consists in using a temperature that allows the release of the free radicals to be controlled.
  • the reaction temperature is regulated such that it is between ambient temperature and 150° C., preferably between 50 and 120° C. and more preferentially between 60 and 100° C.
  • the reaction does not need an initiator, especially for substrates whose double bond bears a chalcogen, usually an oxygen.
  • a free-radical generator still improves the reaction yield.
  • the amount of substrate relative to the sulfonyl chloride is about once the molar amount.
  • this value corresponds to the stoichiometric value as defined by the following reaction:
  • the pressure may vary within large proportions but it is preferable to work at an autogenous pressure or at atmospheric pressure.
  • solvents that may be used are solvents that are inert toward sulfonyl chloride and that do not constitute free-radical traps.
  • alkanes with a suitable boiling point i.e. whose boiling point is at least equal to the temperature at which it is desired to work; petroleum fractions; aromatic chloro derivatives, are all entirely acceptable.
  • sulfonyl chlorides that are preferred are those corresponding to the formula R f —SO 2 —Cl in which R f corresponds to formula (IV):
  • the radicals X which may be similar (i.e. they are identical) or different, represent a chlorine, a fluorine or a radical of formula C n F 2n+1 with n being an integer not more than 5 and preferably not more than 2, with the condition that at least one of the radicals X is fluorine; when p is equal to 1,
  • EWG is an electron-withdrawing group (that is to say that the Hammett constant sigma p is >0, advantageously at least equal to 0.2), otherwise it may be any radical, which is preferably inert, and advantageously an electron-withdrawing group (cf. preceding lines);
  • p is a positive integer, i.e. it cannot comprise the value 0.
  • EWG is advantageously fluorine, especially when p is less than or equal to 2.
  • radicals X are advantageously all fluorine, especially when p is less than or equal to 2.
  • EWG electron-withdrawing group
  • p represents an integer advantageously not more than 4 and preferably not more than 2;
  • EWG advantageously represents an electron-withdrawing group whose optional functions are inert under the reaction conditions, advantageously fluorine or a perfluoro residue of formula C n F 2n+1 , with n being an integer not more than 8 and advantageously not more than 5.
  • the total carbon number of Rf is advantageously between 1 and 15 and preferably between 1 and 10.
  • Rf should be of formula C r F 2r+1 with r being an integer not more than 15 and advantageously between 1 and 10.
  • the present invention is particularly advantageous for radicals R f of low molecular weight, i.e. those that are relatively volatile (with a boiling point at atmospheric pressure of not more than 100° C.).
  • the technique is particularly advantageous for radicals R f containing a radical with an odd number of carbons, and particular mention should be made for radicals R f of C 1 , C 2 and C 3 .
  • Radicals R f higher than C 6 are less advantageous.
  • Z is of structure Y—R 4 with Y being a chalcogen, preferably a light chalcogen, i.e. sulfur or oxygen and more particularly the latter.
  • R 4 is a hydrocarbyl group, i.e. a group containing hydrogen and carbon.
  • These hydrocarbyl groups may be alkyl (i.e. an alcohol residue of which the hydroxyl function is ignored), an aryl or an oxygenated acid residue (i.e. a residue whose acidic hydrogen is borne by an oxygen) from which an OH function has been removed.
  • alkyl i.e. an alcohol residue of which the hydroxyl function is ignored
  • an oxygenated acid residue i.e. a residue whose acidic hydrogen is borne by an oxygen
  • R 4 Y(O) q advantageously have a pKa of not more than 10, preferably not more than 8 and more preferentially not more than 6. Acids with a Hammett constant that is greater than or equal to that of perfluoroalkane-sulfonic acids, and especially triflic acid, are not preferred.
  • the group R 4 is advantageously an electron-withdrawing group of the acyl type.
  • the molecule bearing the double bond not to contain a strongly reductive function, or a nucleophilic function capable of reacting with the sulfonyl chloride.
  • the total carbon number of the substrate of formula I is generally not more than 50 (one significant figure) and better still not more than 30.
  • Rf is of the type CX 3 (CX 2 ) s
  • the presence of halogens heavier than fluorine at the other end of the chain Rf liable to give spurious reactions, especially when the chain Rf is short (s less than or equal to 5 and, even, less than or equal to 4).
  • another aim of the present invention is that of providing reaction intermediates that allow novel routes of access.
  • R 1 , R 2 , Z and Rf being chosen from the same values (and with the same preferences) as above, but with the following additional conditions:
  • R 1 and R 2 chosen from hydrogen and hydrocarbyl radicals, with the condition that one of the radicals R 1 or R 2 at least is equal to H, and advantageously both of them;
  • the possible aromatic nucleus (nuclei) being separated from said double bond by at least two atoms of sp 3 hybridization (in the case of Z, an oxygen atom and at least one carbon atom, advantageously at least two sp 3 carbon atoms; in the other cases, at least two sp 3 carbon atoms);
  • the total carbon number of the molecule being at least equal to (6 ⁇ m) and not more than 30, and advantageously in which:
  • Y is a chalcogen, advantageously a light chalcogen, preferably oxygen;
  • R′ represents a hydrocarbyl, advantageously of not more than four carbons, or preferably a hydrogen
  • m is equal to 1 or, preferably, to zero;
  • R 4 is chosen from hydrocarbyl groups, advantageously from acyls.
  • Rf is of formula C r F 2r+1 with r being an integer not more than 15, advantageously between 1 and 10 and preferably not more than 4.
  • said acid R 4 —YH not to comprise any branching alpha or beta to the atom bearing the acidic proton, in general oxygen; thus, for example, in the case of a carboxylic acid, the atom bearing the carboxylic function, which is beta to the oxygen bearing the proton, is advantageously neither tertiary nor even secondary, nor does it correspond to the branching of an aromatic nucleus.
  • One subfamily of the above compounds is particularly novel, namely the family in which m is equal to zero; when R 3 is other than H, the compounds are highly reactive [lacuna] constitutes only reaction intermediates but remains identifiable, especially at low temperature by fluorine-19 NMR. When R 3 is hydrogen, these compounds are surprisingly stable. These two subfamilies decompose or are hydrolyzed to carbonyl, aldehyde or ketone derivatives, see the examples. This subfamily may thus be used to synthesize by hydrolysis, for example acid hydrolysis, aldehydes or ketones and derivatives thereof. A subsequent oxidation, which is known per se, of the aldehydes gives the corresponding acids.
  • Another advantageous subfamily lies in the alcohol and the corresponding esters in which m is equal to one and Y is oxygen and in which, advantageously, R 3 is H.
  • the alcohol is readily synthesized by alcoholysis of the corresponding ester, without touching the chlorine borne by the carbon atom adjacent to that bearing the ester function and then the alcohol:
  • the alcohol or ester readily lead, especially under the action of strong base (sodium hydroxide, potassium hydroxide or quaternary ammonium hydroxide), the associated acid of which has a pKa at least equal to 12 and advantageously to 13, to epoxides:
  • Sub- Sub- DC RY Test (a) strate R Initiator t(h) strate % (b) % (b) RON 5 OCOC 9 H 19 (PhCO 2 ) 2 13.5 1/1 82 41 240B BJ 540A OCOC 9 H 19 (PhCO 2 ) 2 7 1/1 77 45 BJ 544B OCOC 9 H 19 AIBN 17 1/1.2 76.5 50 BJ 545A OCOC 9 H 19 AIBN 7 1/1.2 75.5 50 BOA 137 (12) OCOCH 3 AIBN 7 1/1 82 52.5 BOA 9 (13) (CH 2 ) 7 CH 3 AIBN 7 1/1.1 91 77.5
  • acyl herein is such that Ac—O— is a propionate
  • the system is cooled in a bath of cardice. Monitoring by GC indicates the end of the reaction.
  • the medium is two-phase and yellow.
  • the lower phase is separated out by settling.
  • a second batch is carried out (30 minutes with stirring at 520 rpm).
  • the intermediate (78) was detected by working at lower temperature and by analyzing the reaction medium after reaction for 1 to 3 hours: (1)/ t DC % (1) DC % (74) RY (78) RY (82) Test (74) ⁇ ° C. (h) % (b) % (a) % (b) % (b) BJ665 1/1 80 1 60 65 28.5 7.5 2 68 75.5 21 19 BJ666 1/1 90 1 69 78 20 23 2 72 90 5 39 3 76 >95 1 39.5

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  • 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)
US10/203,075 2000-02-11 2001-02-12 Method for functionalising a double bond Abandoned US20030114721A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/740,802 US20040147789A1 (en) 2000-02-11 2003-12-22 Allyl esters substituted by a difluoromethylene group, their process of synthesis and their use, and a process for functionalizing a double bond
US10/866,586 US7230147B2 (en) 2000-02-11 2004-06-11 Process for functionalizing a double bond

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0001744A FR2804955B1 (fr) 2000-02-11 2000-02-11 Procede de fonctionnalisation d'une double liaison
FR00/01744 2000-02-11

Related Parent Applications (1)

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PCT/FR2001/000364 A-371-Of-International WO2001058833A1 (fr) 2000-02-11 2001-02-12 Procede de fonctionnalisation d'une double liaison

Related Child Applications (2)

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US10/740,802 Continuation-In-Part US20040147789A1 (en) 2000-02-11 2003-12-22 Allyl esters substituted by a difluoromethylene group, their process of synthesis and their use, and a process for functionalizing a double bond
US10/866,586 Continuation US7230147B2 (en) 2000-02-11 2004-06-11 Process for functionalizing a double bond

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US (2) US20030114721A1 (fr)
EP (1) EP1254091A1 (fr)
JP (1) JP2003522743A (fr)
AU (1) AU2001235628A1 (fr)
CA (1) CA2397834A1 (fr)
FR (1) FR2804955B1 (fr)
HU (1) HUP0204388A2 (fr)
WO (1) WO2001058833A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090105506A1 (en) * 2005-09-29 2009-04-23 Central Glass Company, Limited Process for Producing 3,3,3-Trifluoropropionaldehyde
US20090247786A1 (en) * 2005-11-01 2009-10-01 Central Glass Company, Limited Process For Producing 3,3,3-Trifluoropropionic Acid

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006124282A (ja) * 2004-10-26 2006-05-18 Central Glass Co Ltd ３，３，３−トリフルオロプロピオン酸の製造方法
EP1754697A1 (fr) 2005-08-18 2007-02-21 Solvay S.A. Procédé de préparation d'acides carboxyliques
JP5003072B2 (ja) * 2005-09-29 2012-08-15 セントラル硝子株式会社 ３，３，３−トリフルオロプロピオンアルデヒドの製造方法
JP6041643B2 (ja) * 2012-11-30 2016-12-14 関東電化工業株式会社 ３，３，３−トリフルオロプロピオニル化合物の製造方法
TW201437211A (zh) * 2013-03-01 2014-10-01 Bayer Pharma AG 經取代咪唑并嗒□
CN107108390B (zh) * 2014-11-07 2018-09-14 隆萨有限公司 通过均相催化制备氟烷基化化合物、氯烷基化化合物和氟氯烷基化化合物的方法
JP6632129B2 (ja) * 2016-02-22 2020-01-15 国立大学法人山口大学 α−トリフルオロメチルケトン化合物の製造方法
CN111484407B (zh) * 2019-01-25 2023-04-07 新发药业有限公司 一种1-卤代-2-甲基-4-取代羰基氧基-2-丁烯的制备方法

Family Cites Families (5)

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DE904263C (de) 1941-10-31 1954-02-18 Mueller Fritz Pressenfab Fuehrungslager fuer die Saeulen oder Staender der beweglichen Mittelstuecke von Pressen od. dgl.
DE849061C (de) 1951-03-07 1952-09-11 Hans Biller Fahrspielzeug, insbesondere Spielzeugauto
GB849061A (en) * 1955-09-06 1960-09-21 Minnesota Mining & Mfg Improvements in fluorocarbon-radical-containing organic compounds
GB904263A (en) * 1958-08-11 1962-08-29 Minnesota Mining & Mfg Perfluoroalkyl alkanols
US5773538A (en) * 1997-07-16 1998-06-30 E. I. Du Pont De Nemours And Company Process for polymerization of olefinic monomers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090105506A1 (en) * 2005-09-29 2009-04-23 Central Glass Company, Limited Process for Producing 3,3,3-Trifluoropropionaldehyde
US7544844B2 (en) 2005-09-29 2009-06-09 Central Glass Company, Limited Process for producing 3,3,3-trifluoropropionaldehyde
US20090247786A1 (en) * 2005-11-01 2009-10-01 Central Glass Company, Limited Process For Producing 3,3,3-Trifluoropropionic Acid
US7880033B2 (en) 2005-11-01 2011-02-01 Central Glass Company, Limited Process for producing 3,3,3-trifluoropropionic acid

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CA2397834A1 (fr) 2001-08-16
US7230147B2 (en) 2007-06-12
WO2001058833A1 (fr) 2001-08-16
US20040225160A1 (en) 2004-11-11
EP1254091A1 (fr) 2002-11-06
HUP0204388A2 (en) 2003-05-28
AU2001235628A1 (en) 2001-08-20
JP2003522743A (ja) 2003-07-29
FR2804955B1 (fr) 2003-02-14
FR2804955A1 (fr) 2001-08-17

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