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Sources of Organic Reagents
Appendix2 Source so f Organi cReagent s
The most complete listing of chemicals in commerce is " C h e m Sources" published annually by the Directories Publishing Company, Flemington, New Jersey. This volume lists by name all commercially available chemicals with addresses of suppliers. Of more immediate use for the organic chemist is the remarkable compilation by L. F. Fieser and M. Fieser, "Reagents for Organic Synthesis," Wiley/Interscience. As of this writing, Volume 1 (1967) and Volume 2 (1969) have appeared, and future volumes are anticipated. In their usual thoroughgoing style, the Fiesers have listed hundreds of organic reagents, brief discussions of their sources and applications, and many literature references. Listed below are the organic compounds required for the synthetic experiments in this volume. The three main suppliers of organic reagents are indicated as follows: EK Eastma n Organi cChemicals ,Rochester , N.Y . MC B Matheso n Colema n an d Bell , Norwood , Ohi o A Aldric h Chemica lCompany ,Milwaukee ,Wisconsi n
Other suppliers are listed by name. The reference in parentheses following the name of the compound is to an experi mental procedure for the preparation of that compound. Chapte r 1 I.4-/-Butylcyclohexanol :A 4-Benzoyloxycyclohexano l(Chapte r 7 ,Sectio n X ) Chromiu m trioxide-pyridin ecomple x (Chapte r 1 ,Sectio n I) :E K II .Camphene :EK ,MCB ,A III ./-Buty lperbenzoate :MC B IV .Cholestery lacetate :EK ,MC B VI .Lea d tetraacetate :MC B Cyclooctanol :A VII .Nitrosy lchloride :Matheso n Co . VIII .Rutheniu m dioxide :Alph aInorganics ,Inc . Trichloroisocyanuri caci d (Chapte r 17 ,Sectio n IV) :Chemical sProcuremen t Laboratories , CollegePoint , N.Y . IX .Tetralin :EK ,MC B X .Lea d tetraacetate : MC B Dicarboxyli cacid s(Chapte r 8 ,Section sI I an d IV ) X L Seleniu m dioxide :MC B
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A2 .SOURCE S O FORGANI C REAGENT
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Chapte r 2 I.Diethy ladipate :EK ,MC B /ra«s-9-Decalincarboxyli caci d (Chapte r 16 ,Sectio n I ) Cyclohexanecarboxyli cacid :EK ,A II .4-/-Butylcyclohexanon e(Chapte r1 ,Sectio n I) :A l,4-Dioxaspiro[4.5]decan e(Chapte r 7 ,Sectio n IX ) III .4-r-Butylcyclohexanon e(Chapte r 1 ,Sectio n I) :A Iridiu m tetrachloride :Chemical sProcuremen t Laboratories Goldsmit h Chemica lan d Meta lCorporation ,Evanston ,111 . IV .Chromiu m (III )sulfate :MC B Diethy lfumarate :E K
,Colleg ePoint , N.Y ; D.F .
Chapte r 3 I.Ethylamine ,anhydrous :E K Dimethylamine ,anhydrous :E K Lithiu m wire :MC B II .Ethylenediamine :EK ,MC B Lithiu m wire :MC B III . Δ -Octalone- 2(Chapte r 9 ,Sectio n III ) Lithiu m wire :MC B Ammonia ,anhydrous :Matheso n Co . 10-Methyl-J -octalone- 2(Chapte r 10 ,Sectio n VI ) IV .Hexamethylphosphori ctriamid e (HMPT) :E K Lithiu m wire :MC B Mesity l oxide :EK ,MC B Pulegone :A 1(9)
1(9)
Chapte r 4 I. Diglyme ,bis(2-methoxyethyl )ether :EK ,A Boro n trifluorid eetherate :EK ,MC B Methylenecyclohexan e(Chapte r 7 ,Sectio n I ;Chapte r 11 ,Section sI I an d III) :A 4-Methyl-l-pentene : A ,MC B Norbornene :MC B (-)-a-Pinene :A c/s-2-Butene :Matheso n Co . II .2-Methyl-2-butene :EK ,MC B Boro n trifluorid eetherate :EK ,MC B Diglyme :EK ,A 1-Octyne :Chemical sProcuremen t Laboratories ,Colleg ePoint , N.Y . Limonene :EK ,MC B 4-Vinylcyclohexene :MCB ,A III .Octalin s(Chapte r 3 ,Section sI an d II ;Chapte r 7 ,Sectio n III ) BM B (Chapte r 4 ,Sectio n II ) Chapte r 5 I.Dicyclopentadiene :MCB ,EK Platinu m oxide :MC B II . 5%Rhodiu m o n alumina :MC B III . 5%Rhodiu m o n alumina :MC B
SOURCE S O FORGANI C REAGENT
S
IV . Rhodiu m chloride :MCB , Alph aInorganic s Palladiu m chloride :MCB ,Alph aInorganic s Dowther m A : Do w Chemica l Co . V . Rhodiu m chloride :MCB ,Alph aInorganic s Ergosterol : A ,EK ,MC B Gerany lacetate :A jS-Nitrostyrene :A Methy l oleate : MCB ,E K Naphthoquinone :EK ,MC B Chapte r 6 IV . Cholestanone :A Lithiu m Carbonate :MC B V.1,4-Cyclohexanedio l(Chapte r 5 ,Sectio n II) :E K Chapte r 7 I.A^N-Dimethylcyclohexylmethylamin e(Chapte r 2 ,Sectio n I ) III .2-Decalo l(decahydro-2-naphthol) :A IV .Boro n trifluoride-aceti caci d complex :Harsha w Chemica l Co. ,Allie d Chemica l Co . V.1,5-Cyclooctadiene : A ,MC B Sulfu r dichloride :MC B VI . Boro n trifluorid eetherate :EK ,MC B VII .Mercuri cacetate :MC B Norbornene :MC B VIII .Calciu m carbide :MC B Pinacol:EK ,MC B X .1,4-Cyclohexanedio l(Chapte r 5 ,Sectio n II) : E K XI .Ferrocene : MCB ,A Λ-Butyllithium : Foot eMinera l Co. ,Alph aInorganic s Amy lnitrate : Κ+ ΚLaboratories , Lo sAngele s XII .Boro n tribromide :MC B Methy lethers :A Chapte r 8 I.1,4-Diphenyl-1,3-butadien e(Chapte r 11 ,Sectio n I) :A II .1,3-Butadiene :Matheso n Co . 3-Sulfolen e(2,5-dihydrothiophene-1, 1 -dioxide) :EK ,MC B IV .Isopropeny lacetate :MC B Dimedon :EK ,MC B 1,3-Cyclohexanedion e(Chapte r 5 ,Sectio n II) :A 2-Cyclohexen-l-one :A V . Dicyclopentadiene : MCB ,E K Chapte r 9 I.Morpholine :MCB ,E K II .1-Morpholino-l-cyclohexen e(Chapte r 9 ,Sectio n I) :A III .Methy lviny l ketone : MCB ,A 1-Morpholino-l-cyclohexen e(Chapte r 9 ,Sectio n I) :A IV . 0-Propiolactone :EK ,MC B 1-Morpholino-l-cyclohexen e(Chapte r 9 ,Sectio n I) :A V . Acrolein :EK ,MC B Pyrrolidine : MCB ,E K
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Chapte r1 0 I.Sodiu m hydride , 50 % dispersio n i n minera l oil :Alph aInorganic s Ethy lchloroformate :EK ,MC B III .Sodiu m hydride , 50 % dispersio n i n minera l oil :Alph aInorganic s VI .Ethy l5-bromovalerate :A Sodiu m hydride , 50 % dispersio n i n minera l oil :Alph aInorganic s 2-Carbethoxycyclooctanon e(Chapte r 10 ,Sectio n I ) VII .2-Methylcyclohexanone : A ,E K Methy lviny lketone :MCB ,A Chapte r1 1 II .Methy lbromide ,ampoule :E K /i-Butyllithium : Foot eMineral Co. ,Alph aInorganic s III .Sodiu m hydride , 50 % dispersio n i n minera l oil :Alph aInorganic s IV .Ethylen e oxide :Matheso n Co . V . α-Bromo-y-butyrolactone:A Sodiu m amide :MC B Chapte r1 2 I.Carbo n monoxide :Matheso n Co . Diglyme :EK ,MC B Norbornene :MC B Boro n trifluorid eetherate :EK ,MC B II .(Se eI above ) III .(Se eI above ) Methy lviny lketone :MCB ,A 1-Octene :A IV . Potassium/-butoxide :MC B Chapte r1 3 I.Zinc-coppe r coupl e(Chapte r 13 ,Sectio n I) :Alph aInorganic s II . Potassium/-butoxide :MC B m-Cyclooctene : A ,MC B III .Sodiu m trichloroacetate :E K Phenylmercuri cchloride : A ,Alph aInorganics ,MC B Phenyl(trichloromethyl)mercury :E K Chapte r1 4 I. Ammonia ,anhydrous :Matheso n Co . Acetylene :Matheso n Co . II .Hexamethylphosphori cTriamid e (HMPT) :MCB , A ,E K Acetylene :Matheso n Co . III .(Se eChapte r 10 ,Sectio n III ) Triphenylmethane :EK ,MC B Acetylene :Matheso n Co . Chapte r1 5 I.Tetrahydrodicyclopentadien e(Chapte r 5 ,Sectio n I) :A II .Campho r quinon e(Chapte r1 ,Sectio n XI) :A p-Toluenesulfonylhydrazide : A ,E K
SOURCE S O FORGANI C REAGENT
S
165
III .1-Ethynylcyclohexano l(Chapte r 14 ,Sectio n I) :MC B Dowex-5 0resin : Do w Chemica l Co. ,availabl efro m J .T .Bake r Chemica l Co . IV .1,5-Cyclooctadiene : A ,MC B V .2-Acetylcyclohexanon e(Chapte r 9 ,Sectio n II) :Chemical sProcuremen t Laboratories CollegePoint , N.Y . VII .Methyllithium ,2 Μi n ether : Alph aInorganic s Chapte r1 6 I.2-Methylcyclohexanol :E K Decahydro-2-naphthol :A II . α-Bromo-p-xylene: A ,EK ,MC B Trimethylamine ,anhydrous : E K Phenothiazine :EK ,MC B V .Dibenzy l ketone :EK ,MC B Triethylamine : MCB ,E K VI .Olefins :A VII .Cyclohexanecarbony lchloride :E K Triethylamine : MCB , E K VIII .7V-Methyl-iV-nitroso -/7-toluenesulfonamide :A IX . Isophorone : MCB ,A J -Octalone- 2(Chapte r 9 ,Sectio n III ) X .Sodiu m hydride , 50 % dispersio n i n minera l oil : Alph aInorganic s Trimethyloxosulfoniu m iodid e(trimethylsulfoxoniu m iodide) : A , E K 1(9)
Chapte r1 7 I.Adamantan e(Chapte r 15 ,Sectio n I) :A 1-Bromoadamantan e(Chapte r 17 ,Sectio n I) :A III .iV-Methyl-^V-nitroso-p-toluenesulfonamide :A IV .Cyanuri cacid : A ,EK ,MC B
,
The most complete listing of chemicals in commerce is " C h e m Sources" published annually by the Directories Publishing Company, Flemington, New Jersey. This volume lists by name all commercially available chemicals with addresses of suppliers. Of more immediate use for the organic chemist is the remarkable compilation by L. F. Fieser and M. Fieser, "Reagents for Organic Synthesis," Wiley/Interscience. As of this writing, Volume 1 (1967) and Volume 2 (1969) have appeared, and future volumes are anticipated. In their usual thoroughgoing style, the Fiesers have listed hundreds of organic reagents, brief discussions of their sources and applications, and many literature references. Listed below are the organic compounds required for the synthetic experiments in this volume. The three main suppliers of organic reagents are indicated as follows: EK Eastma n Organi cChemicals ,Rochester , N.Y . MC B Matheso n Colema n an d Bell , Norwood , Ohi o A Aldric h Chemica lCompany ,Milwaukee ,Wisconsi n
Other suppliers are listed by name. The reference in parentheses following the name of the compound is to an experi mental procedure for the preparation of that compound. Chapte r 1 I.4-/-Butylcyclohexanol :A 4-Benzoyloxycyclohexano l(Chapte r 7 ,Sectio n X ) Chromiu m trioxide-pyridin ecomple x (Chapte r 1 ,Sectio n I) :E K II .Camphene :EK ,MCB ,A III ./-Buty lperbenzoate :MC B IV .Cholestery lacetate :EK ,MC B VI .Lea d tetraacetate :MC B Cyclooctanol :A VII .Nitrosy lchloride :Matheso n Co . VIII .Rutheniu m dioxide :Alph aInorganics ,Inc . Trichloroisocyanuri caci d (Chapte r 17 ,Sectio n IV) :Chemical sProcuremen t Laboratories , CollegePoint , N.Y . IX .Tetralin :EK ,MC B X .Lea d tetraacetate : MC B Dicarboxyli cacid s(Chapte r 8 ,Section sI I an d IV ) X L Seleniu m dioxide :MC B
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A2 .SOURCE S O FORGANI C REAGENT
S
Chapte r 2 I.Diethy ladipate :EK ,MC B /ra«s-9-Decalincarboxyli caci d (Chapte r 16 ,Sectio n I ) Cyclohexanecarboxyli cacid :EK ,A II .4-/-Butylcyclohexanon e(Chapte r1 ,Sectio n I) :A l,4-Dioxaspiro[4.5]decan e(Chapte r 7 ,Sectio n IX ) III .4-r-Butylcyclohexanon e(Chapte r 1 ,Sectio n I) :A Iridiu m tetrachloride :Chemical sProcuremen t Laboratories Goldsmit h Chemica lan d Meta lCorporation ,Evanston ,111 . IV .Chromiu m (III )sulfate :MC B Diethy lfumarate :E K
,Colleg ePoint , N.Y ; D.F .
Chapte r 3 I.Ethylamine ,anhydrous :E K Dimethylamine ,anhydrous :E K Lithiu m wire :MC B II .Ethylenediamine :EK ,MC B Lithiu m wire :MC B III . Δ -Octalone- 2(Chapte r 9 ,Sectio n III ) Lithiu m wire :MC B Ammonia ,anhydrous :Matheso n Co . 10-Methyl-J -octalone- 2(Chapte r 10 ,Sectio n VI ) IV .Hexamethylphosphori ctriamid e (HMPT) :E K Lithiu m wire :MC B Mesity l oxide :EK ,MC B Pulegone :A 1(9)
1(9)
Chapte r 4 I. Diglyme ,bis(2-methoxyethyl )ether :EK ,A Boro n trifluorid eetherate :EK ,MC B Methylenecyclohexan e(Chapte r 7 ,Sectio n I ;Chapte r 11 ,Section sI I an d III) :A 4-Methyl-l-pentene : A ,MC B Norbornene :MC B (-)-a-Pinene :A c/s-2-Butene :Matheso n Co . II .2-Methyl-2-butene :EK ,MC B Boro n trifluorid eetherate :EK ,MC B Diglyme :EK ,A 1-Octyne :Chemical sProcuremen t Laboratories ,Colleg ePoint , N.Y . Limonene :EK ,MC B 4-Vinylcyclohexene :MCB ,A III .Octalin s(Chapte r 3 ,Section sI an d II ;Chapte r 7 ,Sectio n III ) BM B (Chapte r 4 ,Sectio n II ) Chapte r 5 I.Dicyclopentadiene :MCB ,EK Platinu m oxide :MC B II . 5%Rhodiu m o n alumina :MC B III . 5%Rhodiu m o n alumina :MC B
SOURCE S O FORGANI C REAGENT
S
IV . Rhodiu m chloride :MCB , Alph aInorganic s Palladiu m chloride :MCB ,Alph aInorganic s Dowther m A : Do w Chemica l Co . V . Rhodiu m chloride :MCB ,Alph aInorganic s Ergosterol : A ,EK ,MC B Gerany lacetate :A jS-Nitrostyrene :A Methy l oleate : MCB ,E K Naphthoquinone :EK ,MC B Chapte r 6 IV . Cholestanone :A Lithiu m Carbonate :MC B V.1,4-Cyclohexanedio l(Chapte r 5 ,Sectio n II) :E K Chapte r 7 I.A^N-Dimethylcyclohexylmethylamin e(Chapte r 2 ,Sectio n I ) III .2-Decalo l(decahydro-2-naphthol) :A IV .Boro n trifluoride-aceti caci d complex :Harsha w Chemica l Co. ,Allie d Chemica l Co . V.1,5-Cyclooctadiene : A ,MC B Sulfu r dichloride :MC B VI . Boro n trifluorid eetherate :EK ,MC B VII .Mercuri cacetate :MC B Norbornene :MC B VIII .Calciu m carbide :MC B Pinacol:EK ,MC B X .1,4-Cyclohexanedio l(Chapte r 5 ,Sectio n II) : E K XI .Ferrocene : MCB ,A Λ-Butyllithium : Foot eMinera l Co. ,Alph aInorganic s Amy lnitrate : Κ+ ΚLaboratories , Lo sAngele s XII .Boro n tribromide :MC B Methy lethers :A Chapte r 8 I.1,4-Diphenyl-1,3-butadien e(Chapte r 11 ,Sectio n I) :A II .1,3-Butadiene :Matheso n Co . 3-Sulfolen e(2,5-dihydrothiophene-1, 1 -dioxide) :EK ,MC B IV .Isopropeny lacetate :MC B Dimedon :EK ,MC B 1,3-Cyclohexanedion e(Chapte r 5 ,Sectio n II) :A 2-Cyclohexen-l-one :A V . Dicyclopentadiene : MCB ,E K Chapte r 9 I.Morpholine :MCB ,E K II .1-Morpholino-l-cyclohexen e(Chapte r 9 ,Sectio n I) :A III .Methy lviny l ketone : MCB ,A 1-Morpholino-l-cyclohexen e(Chapte r 9 ,Sectio n I) :A IV . 0-Propiolactone :EK ,MC B 1-Morpholino-l-cyclohexen e(Chapte r 9 ,Sectio n I) :A V . Acrolein :EK ,MC B Pyrrolidine : MCB ,E K
163
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A2 .SOURCE S O FORGANI C REAGENT
S
Chapte r1 0 I.Sodiu m hydride , 50 % dispersio n i n minera l oil :Alph aInorganic s Ethy lchloroformate :EK ,MC B III .Sodiu m hydride , 50 % dispersio n i n minera l oil :Alph aInorganic s VI .Ethy l5-bromovalerate :A Sodiu m hydride , 50 % dispersio n i n minera l oil :Alph aInorganic s 2-Carbethoxycyclooctanon e(Chapte r 10 ,Sectio n I ) VII .2-Methylcyclohexanone : A ,E K Methy lviny lketone :MCB ,A Chapte r1 1 II .Methy lbromide ,ampoule :E K /i-Butyllithium : Foot eMineral Co. ,Alph aInorganic s III .Sodiu m hydride , 50 % dispersio n i n minera l oil :Alph aInorganic s IV .Ethylen e oxide :Matheso n Co . V . α-Bromo-y-butyrolactone:A Sodiu m amide :MC B Chapte r1 2 I.Carbo n monoxide :Matheso n Co . Diglyme :EK ,MC B Norbornene :MC B Boro n trifluorid eetherate :EK ,MC B II .(Se eI above ) III .(Se eI above ) Methy lviny lketone :MCB ,A 1-Octene :A IV . Potassium/-butoxide :MC B Chapte r1 3 I.Zinc-coppe r coupl e(Chapte r 13 ,Sectio n I) :Alph aInorganic s II . Potassium/-butoxide :MC B m-Cyclooctene : A ,MC B III .Sodiu m trichloroacetate :E K Phenylmercuri cchloride : A ,Alph aInorganics ,MC B Phenyl(trichloromethyl)mercury :E K Chapte r1 4 I. Ammonia ,anhydrous :Matheso n Co . Acetylene :Matheso n Co . II .Hexamethylphosphori cTriamid e (HMPT) :MCB , A ,E K Acetylene :Matheso n Co . III .(Se eChapte r 10 ,Sectio n III ) Triphenylmethane :EK ,MC B Acetylene :Matheso n Co . Chapte r1 5 I.Tetrahydrodicyclopentadien e(Chapte r 5 ,Sectio n I) :A II .Campho r quinon e(Chapte r1 ,Sectio n XI) :A p-Toluenesulfonylhydrazide : A ,E K
SOURCE S O FORGANI C REAGENT
S
165
III .1-Ethynylcyclohexano l(Chapte r 14 ,Sectio n I) :MC B Dowex-5 0resin : Do w Chemica l Co. ,availabl efro m J .T .Bake r Chemica l Co . IV .1,5-Cyclooctadiene : A ,MC B V .2-Acetylcyclohexanon e(Chapte r 9 ,Sectio n II) :Chemical sProcuremen t Laboratories CollegePoint , N.Y . VII .Methyllithium ,2 Μi n ether : Alph aInorganic s Chapte r1 6 I.2-Methylcyclohexanol :E K Decahydro-2-naphthol :A II . α-Bromo-p-xylene: A ,EK ,MC B Trimethylamine ,anhydrous : E K Phenothiazine :EK ,MC B V .Dibenzy l ketone :EK ,MC B Triethylamine : MCB ,E K VI .Olefins :A VII .Cyclohexanecarbony lchloride :E K Triethylamine : MCB , E K VIII .7V-Methyl-iV-nitroso -/7-toluenesulfonamide :A IX . Isophorone : MCB ,A J -Octalone- 2(Chapte r 9 ,Sectio n III ) X .Sodiu m hydride , 50 % dispersio n i n minera l oil : Alph aInorganic s Trimethyloxosulfoniu m iodid e(trimethylsulfoxoniu m iodide) : A , E K 1(9)
Chapte r1 7 I.Adamantan e(Chapte r 15 ,Sectio n I) :A 1-Bromoadamantan e(Chapte r 17 ,Sectio n I) :A III .iV-Methyl-^V-nitroso-p-toluenesulfonamide :A IV .Cyanuri cacid : A ,EK ,MC B
,