591-97-9

Basic information

• Product Name: 1-Chloro-2-butene
• Synonyms: (2E)-1-Chloro-2-butene;1-chloro-2-buten;1-chloro-but-2-ene;1-chlorobut-2-ene;2-Butene,1-chloro-;2-Butenyl chloride;2-butenylchloride;alpha-Chloro-beta-butylene
• CAS NO: 591-97-9
• Molecular Formula: C₄H₇Cl
• Molecular Weight: 90.55
• EINECS: 209-739-5
• Mol File: 591-97-9.mol
• Article Data: 8

Chemical Properties

• Melting Point: -65°C
• Boiling Point: 85-86 °C(lit.)
• Flash Point: -12°C
• Appearance: colourless liquid
• Density: 0.923 g/mL at 20 °C(lit.)
• Vapor Pressure: 80.6mmHg at 25°C
• Refractive Index: n20/D 1.430
• Storage Temp.: 0-6°C
• Solubility: water: soluble14g/L at 20°C
• Water Solubility: 999mg/L(temperature not stated)
• Stability: Stable. Highly flammable. Incompatible with strong oxidizing agents.
• Merck: 14,2130
• BRN: 605304
• CAS DataBase Reference: 1-Chloro-2-butene(CAS DataBase Reference)
• NIST Chemistry Reference: 1-Chloro-2-butene(591-97-9)
• EPA Substance Registry System: 1-Chloro-2-butene(591-97-9)

Safety Data

• Hazard Codes: F,C
• Statements: 11-22-34-43
• Safety Statements: 16-26-36/37/39-45
• RIDADR: UN 2924 3/PG 2
• WGK Germany: 2
• RTECS: EM4264000
• F: 19
• HazardClass: 3
• PackingGroup: II
• Hazardous Substances Data: 591-97-9(Hazardous Substances Data)

Usage

Chemical Properties

colourless liquid

Uses

Crotyl chloride has been used:to investihgate the kinetics of the reactions of atomic chlorine with series of unsaturated aldehydes and ketones at 298K, to probe structure-reactivity relationshipsin the preparation of (E)-crotyltrichlorosilane

General Description

Crotyl chloride reacts with trichlorosilane in the presence of tertiary amine and copper salts to give the corresponding allyltrichlorosilanes.

InChI:InChI=1/C4H7Cl/c1-2-3-4-5/h2-3H,4H2,1H3

Synthetic route

(E/Z)-2-buten-1-ol (6117-91-5) → 1-chloro-2-butene (591-97-9)

Conditions	Yield
With triphenylphosphine In various solvent(s) at 20℃; for 1h;	28%
With hydrogenchloride
With N-chloro-succinimide; dimethylsulfide In dichloromethane
With oxalyl dichloride; Triphenylphosphine oxide In chloroform at 20℃; for 7h;	70 %Spectr.
With oxalyl dichloride; chloro(triphenyl)phosphonium chloride In chloroform at 20℃; for 7h; Appel reaction;	64 mg

2-hydroxy-3-butene (598-32-3) → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9)

Conditions	Yield
With hydrogenchloride; water
With bismuth(III) chloride In tetrachloromethane for 0.0833333h; Heating;

2-chloro-3-butene (563-52-0) → 1-chloro-2-butene (591-97-9)

Conditions	Yield
With water at 85℃;

(E/Z)-2-buten-1-ol (6117-91-5) → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9)

Conditions	Yield
With hydrogenchloride; water
With bismuth(III) chloride In tetrachloromethane for 0.0833333h; Heating;

1-Methyl-2-propenyl diphenyl phosphate (96233-06-6) → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9)

Conditions	Yield
With lithium chloride In N,N-dimethyl-formamide for 0.166667h; Ambient temperature; Yield given. Yields of byproduct given;

hydrogenchloride (7647-01-0) + buta-1,3-diene (106-99-0) → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9)

hydrogenchloride (7647-01-0) + acetic acid (64-19-7) + buta-1,3-diene (106-99-0) → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9)

Conditions	Yield
at 25℃;
at 25℃;

1-butylene (106-98-9) + chlorine (7782-50-5) → 2-chloro-3-butene (563-52-0) + 1,1-dichlorobutane (541-33-3) + 1,1-dichloro-but-2-ene (51157-81-4) + 1-chloro-2-butene (591-97-9)

Conditions	Yield
at 380 - 390℃;

hydrogenchloride (7647-01-0) + 2-chloro-3-butene (563-52-0) → 1-chloro-2-butene (591-97-9)

Conditions	Yield
reagiert analog mit CuCl, FeCl3;
reagiert analog in Gegenwart von CuCl, FeCl3; Gleichgewichte der Reaktion;

2-chloro-3-butene (563-52-0) + water (7732-18-5) → 1-chloro-2-butene (591-97-9)

Conditions	Yield
at 85℃;

hydrogenchloride (7647-01-0) + (E/Z)-2-buten-1-ol (6117-91-5) → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9)

Conditions	Yield
Bei der Einwaermen;

hydrogenchloride (7647-01-0) + 2-hydroxy-3-butene (598-32-3) → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9)

trans-but-2-enyl chloride (4894-61-5) + copper (I)-chloride → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9)

Conditions	Yield
at 60℃;

2-hydroxy-3-butene (598-32-3) → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9) + (but-2-enyl)(1-methylprop-2-enyl) ether

Conditions	Yield
With bismuth(III) chloride In tetrachloromethane at 25℃; for 1.5h;

(E/Z)-2-buten-1-ol (6117-91-5) → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9) + (but-2-enyl)(1-methylprop-2-enyl) ether

Conditions	Yield
With bismuth(III) chloride In tetrachloromethane at 25℃; for 1h;

(3-methylallyloxy)dichloroborane → 2-chloro-3-butene (563-52-0) + 1-chloro-2-butene (591-97-9)

Conditions	Yield
decompn. rates: 11 % / 3 h, 92 % / 21 h;
decompn. rates: 11 % / 3 h, 92 % / 21 h;

(E/Z)-2-buten-1-ol (6117-91-5) + benzoyl chloride (98-88-4) → crotyl benzoate (88927-00-8, 104664-93-9, 91142-49-3) + 1-chloro-2-butene (591-97-9)

Conditions	Yield
With N,N-dimethyl-formamide at 20℃; for 3h; Cooling with ice;

benzaldehyde (100-52-7) + 1-chloro-2-butene (591-97-9) → 2-methyl-1-phenyl-3-butene-1-ol (25201-44-9)

Conditions	Yield
With indium iodide; triphenylphosphine; bis(acetylacetonate)nickel(II) In various solvent(s) at 20℃; for 1h;	100%
Stage #1: benzaldehyde; 1-chloro-2-butene With tin(II) chloride hydrate; sodium iodide In N,N-dimethyl-formamide at 20℃; for 20h; Stage #2: With ammonium fluoride In diethyl ether; water; N,N-dimethyl-formamide at 20℃; for 0.5h;	93%
With sodium iodide; tin(ll) chloride In N,N-dimethyl-formamide for 20h; Ambient temperature;	89%
With 1,3-dimethyl-2-imidazolidinone; tin(IV) iodide; sodium iodide at 20℃; for 46h;	68%
With ammonium chloride; zinc In tetrahydrofuran; water at 20℃; for 12h; Barbier Coupling Reaction;

1-chloro-2-butene (591-97-9) + 2-Fluoro-2-phenyl-2-phenylthioacetonitrile (210217-98-4) → (E)-2-Fluoro-2-phenyl-hex-4-enenitrile

Conditions	Yield
With Triethylgermyl-natrium In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide 1.) -60 deg C, 0.25 h, 2.) -80 deg C, 0.5 h;	99%

1-chloro-2-butene (591-97-9) + benzyl 2-phenylpropanoate (97479-87-3) → benzyl (4E)-2-methyl-2-phenylhex-4-enoate (847444-10-4)

Conditions	Yield
With lithium iodide; lithium hexamethyldisilazane In tetrahydrofuran at 0 - 25℃; for 18h;	99%

1-chloro-2-butene (591-97-9) + methyl salicylate (119-36-8) → 2-(2-Butenyloxy)-benzoesaeuremethylester (133609-83-3, 133609-97-9)

Conditions	Yield
With potassium carbonate; sodium iodide In acetone for 72h; Heating;	98%

bis(cycloocta-1,5-diene)platinum(0) (12130-66-4) + 1-chloro-2-butene (591-97-9) → [PtCl(σ-CH2CH=CHMe)(cod)]

Conditions	Yield
In Petroleum ether in N2 atm., metal compd. added to soln. of org. compd., last in excess,at room temp. for 15 min; liq. removed from ppt., residue washed with petroleum ether, dried in vac.; elem. anal.;	98%

4-Phenylphenol (92-69-3) + 1-chloro-2-butene (591-97-9) → 1-(but-2-en-1-yloxy)-4-phenylbenzene

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 23℃; for 5h; Alkylation;	97%

1-chloro-2-butene (591-97-9) + 6-(p-tolyl)-4-(trifluoromethyl)pyridin-2(1H)-one → 2-[((E)-But-2-enyl)oxy]-6-p-tolyl-4-trifluoromethyl-pyridine

Conditions	Yield
With potassium carbonate; sodium iodide In acetone for 5h; Heating;	96%

trans-1-(4'-methoxyphenyl)-3-chloro-3-phenylthio-4-phenylazetidin-2-one (94612-26-7) + 1-chloro-2-butene (591-97-9) → 1-(4'-methoxyphenyl)-3-(1'-methylallyl)-3-phenylthio-4-phenylazetidin-2-one

Conditions	Yield
Stage #1: 1-chloro-2-butene With magnesium In diethyl ether at 0℃; Stage #2: With chloro-trimethyl-silane at 0℃; Stage #3: trans-1-(4'-methoxyphenyl)-3-chloro-3-phenylthio-4-phenylazetidin-2-one With titanium tetrachloride In dichloromethane at 0℃; for 2h; Inert atmosphere; stereoselective reaction;	96%

1-chloro-2-butene (591-97-9) + palladium dichloride → crotylpalladium chloride dimer

Conditions	Yield
With hydrogenchloride In water at 30℃; for 20.5h; Temperature; Inert atmosphere;	95.6%

2-(1-methylethyl)phenol (88-69-7) + 1-chloro-2-butene (591-97-9) → 1-[(E)-but-2-enoxy]-2-isopropylbenzene (160592-66-5)

Conditions	Yield
With sodium hydroxide In N,N-dimethyl-formamide at 10 - 15℃; for 5h;	95.08%
With sodium hydroxide In N,N-dimethyl-formamide at 10 - 15℃; for 5h; Inert atmosphere; Industrial scale;	95.08%

1-chloro-2-butene (591-97-9) + palladium dichloride → ϖ-crotyl-Pd Chloride

Conditions	Yield
With sodium chloride In methanol; water for 2h;	94%

chloro-trimethyl-silane (75-77-4) + 1-chloro-2-butene (591-97-9) → (E-1-chlorobut-2-enyl)trimethyl silane (141854-76-4)

Conditions	Yield
With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 2h;	93%

1,2-Dihydro-2-oxo-6-phenyl-4-trifluoromethylpyridine (22122-89-0) + 1-chloro-2-butene (591-97-9) → 2-[((E)-But-2-enyl)oxy]-6-phenyl-4-trifluoromethyl-pyridine

Conditions	Yield
With potassium carbonate; sodium iodide In acetone for 5h; Heating;	93%

4-hydroxy-2-methylanisole (14786-82-4) + 1-chloro-2-butene (591-97-9) → 4-But-2-enyloxy-1-methoxy-2-methyl-benzol (13052-25-0)

Conditions	Yield
With potassium carbonate In acetone Heating;	93%

1-chloro-2-butene (591-97-9) → (E/Z)-2-buten-1-ol (6117-91-5)

Conditions	Yield
With octadecyltrimethylammonium bromide; water; sodium carbonate In pentane at 35℃; pH=6;	92%

benzamide (55-21-0) + 1-chloro-2-butene (591-97-9) → N,N-di(but-2-en-1-yl)benzamide

Conditions	Yield
With sodium hydride; potassium iodide In N,N-dimethyl-formamide; mineral oil at 20℃; for 24h; Inert atmosphere;	92%

1-chloro-2-butene (591-97-9) + 1-trimethylsilylpyrazole (18156-75-7) → (1-pyrazolyl)-1 butene-2 (63935-95-5)

Conditions	Yield
at 100℃; for 12h;	91%

1-chloro-2-butene (591-97-9) + 1-(trimethylsilyl)-1H-benzotriazole (43183-36-4) → (1-benzotriazolyl)-1 butene-2 (63936-03-8)

Conditions	Yield
at 100℃; for 15h;	91%

1-chloro-2-butene (591-97-9) + 6-(4-chloro-phenyl)-4-trifluoromethyl-1H-pyridin-2-one (177098-85-0) → 2-[((E)-But-2-enyl)oxy]-6-(4-chloro-phenyl)-4-trifluoromethyl-pyridine

Conditions	Yield
With potassium carbonate; sodium iodide In acetone for 5h; Heating;	90%

1-chloro-2-butene (591-97-9) + 6-hydroxy-5-oxo-1,2,3,5-tetrahydroindolizine-8-carboxylic acid methyl ester (185198-42-9) → methyl 6-(but-2-enyloxy)-5-oxo-1,2,3,5-tetrahydroindolizine-8-carboxylate

Conditions	Yield
With potassium carbonate In acetone for 18h; Williamson etherification; Heating;	90%

C29H32IrN5O + 1-chloro-2-butene (591-97-9) → [OC-6-53]-(but-2-en-1-yl)carbonylchlorido(1,1'-(3,6-di-tert-butylcarbazol-9-id-1,8-diyl-κN)bis(3-methyl-1H-imidazolin-2-yliden-κ2C2))iridium

Conditions	Yield
In tetrahydrofuran for 0.166667h; Inert atmosphere; Schlenk technique;	90%

1-chloro-2-butene (591-97-9) + tert-butyl 1,4-diazepine-1-carboxylate (112275-50-0) → tert-butyl 4-but-2-enoyl-1,4-diazepane-1-carboxylate

Conditions	Yield
With triethylamine In dichloromethane at 0 - 27℃; for 1h;	90%

1-chloro-2-butene (591-97-9) → but-2-enyltrichlorosilane (18147-55-2)

Conditions	Yield
With trichlorosilane; triethylamine; copper(l) iodide	89%
With trichlorosilane; triethylamine; copper(l) chloride In diethyl ether at 20℃;	88%
With tetrachlorosilane; triethylamine; copper(l) chloride	79%
With trichlorosilane; triethylamine; copper(l) chloride In diethyl ether at 20℃; for 2h;	66%

1-chloro-2-butene (591-97-9) + cyclohexanecarbaldehyde (2043-61-0) → 1-cyclohexyl-2-methylbut-3-en-1-ol (93965-64-1, 93965-65-2, 106650-99-1, 106651-03-0, 121155-51-9, 121155-52-0, 121842-21-5)

Conditions	Yield
With bis(cyclopentadienyl)titanium dichloride; diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In tetrahydrofuran at 20℃; for 12h; Inert atmosphere; Irradiation; regioselective reaction;	89%

dimethyl (prop-2-yn-1-yl)malonate (95124-07-5) + 1-chloro-2-butene (591-97-9) → 2-but-2-enyl-2-prop-2-ynyl-malonic acid dimethyl ester (113704-38-4)

Conditions	Yield
With caesium carbonate In acetone Heating;	88%

1-chloro-2-butene (591-97-9) + 1-trimethylsilyl-1,2,4-triazole (18293-54-4) → (1-triazolyl-1,2,4)-1 butene-2 (63935-99-9)

Conditions	Yield
at 100℃; for 11h;	87%

cyclododecanone (830-13-7) + 1-chloro-2-butene (591-97-9) → 1-(1-Methyl-allyl)-cyclododecanol

Conditions	Yield
With bis(cyclopentadienyl)titanium dichloride; manganese; lithium bromide In tetrahydrofuran at 0℃; Barbier-type crotylation; Inert atmosphere;	87%

1-chloro-2-butene (591-97-9) + 6-Ethyl-4-trifluoromethyl-1H-pyridin-2-one → 2-[((E)-But-2-enyl)oxy]-6-ethyl-4-trifluoromethyl-pyridine

Conditions	Yield
With potassium carbonate; sodium iodide In acetone for 5h; Heating;	86%

1-chloro-2-butene (591-97-9) → (2R,3S)-1-chlorobutane-2,3-diol (177930-71-1)

Conditions	Yield
With AD-mix-α; methanesulfonamide; sodium hydrogencarbonate In water; tert-butyl alcohol at 0℃; for 72h;	86%
With methanesulfonamide; sodium hydrogencarbonate; (9S,9"S)-9,9"-[phthalazine-1,4-diylbis-(oxy)]bis[10,11-dihydro-6'-methoxycinchonane] In water; tert-butyl alcohol at 0 - 4℃; for 72h; Inert atmosphere; Schlenk technique;	82%

1-chloro-2-butene (591-97-9) + dimethylphenyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane (185990-03-8) → CH3CHCHCH(Si(CH3)2(C6H5))B(OC(CH3)2)2

Conditions	Yield
With lithium diisopropyl amide In tetrahydrofuran byproducts: LiCl; chloride, boron compound and LDA mixed in THF at -98°C, stirred for 10 min, warmed to room temp.; E/Z isomers;	86%

Upstream product

• 598-32-3 2-hydroxy-3-butene 
• 6117-91-5 (E/Z)-2-buten-1-ol 
• 98-88-4 benzoyl chloride 
• 68-12-2 N,N-dimethyl-formamide 
• 4894-61-5 trans-but-2-enyl chloride 
• 7647-01-0 hydrogenchloride 
• 563-52-0 2-chloro-3-butene 
• 7732-18-5 water 
• 106-98-9 1-butylene 
• 7782-50-5 chlorine 
• 64-19-7 acetic acid 
• 106-99-0 buta-1,3-diene 
• 96233-06-6 1-Methyl-2-propenyl diphenyl phosphate 

Downstream Products

• 13389-42-9 trans-2-Octene 
• 1541-33-9 3-methyl-1,5-hexadiene 
• 1541-23-7 hepta-1,5-diene 
• 598-32-3 2-hydroxy-3-butene 
• 6117-91-5 (E/Z)-2-buten-1-ol 
• 21035-54-1 crotylamine 
• 30056-32-7 but-2-enyl-(4-nitro-phenyl)-ether 
• 682-34-8 crotyl phosphonate de diethyle 
• 64343-08-4 (1-chloro-2-butanyl)benzene 
• 111712-50-6 2,3-dibromo-1-chloro-butane 
• 18338-40-4 1,2,3-trichloro-butane 
• 106-99-0 buta-1,3-diene 
• 6714-00-7 hept-5-en-2-one 
• 5673-99-4 dimethyl-2,3 penten-4-ol-1 

Relevant articles and documents

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METHOD OF CONVERTING ALCOHOL TO HALIDE

The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.

Phosphine oxide-catalysed chlorination reactions of alcohols under Appel conditions

A phosphine oxide-catalysed chlorination reaction of primary and secondary alcohols has been developed. This process represents the first triphenylphosphine oxide-catalysed alcohol chlorination under Appel conditions. The Royal Society of Chemistry 2010.