1476-11-5

Basic information

• Product Name: cis-1,4-Dichloro-2-butene
• Synonyms: (Z)-1,4-Dichloro-2-butene;(Z)-1,4-Dichlorobutene;1,4-Dichlor-2-butencis;1,4-dichloro-cis-2-butene;2-Butene,1,4-dichloro-,(2Z)-;2-Butene,1,4-dichloro-,(Z)-;4-dichloro-(z)-2-buten;4-dichloro-cis-2-buten
• CAS NO: 1476-11-5
• Molecular Formula: C₄H₆Cl₂
• Molecular Weight: 125
• EINECS: 216-021-5
• Product Categories: API intermediates;All Aliphatics;Aliphatics;Alkenyl;Halogenated Hydrocarbons;Organic Building Blocks;Building Blocks;Chemical Synthesis;Halogenated Hydrocarbons;Organic Building Blocks;Pharmaceutical intermediates
• Mol File: 1476-11-5.mol
• Article Data: 12

Chemical Properties

• Melting Point: −48 °C(lit.)
• Boiling Point: 152 °C758 mm Hg(lit.)
• Flash Point: 132 °F
• Appearance: Clear colorless to yellow/Liquid
• Density: 1.188 g/mL at 25 °C(lit.)
• Refractive Index: n20/D 1.489(lit.)
• Storage Temp.: 2-8°C
• Solubility: Chlorform (Sparingly), Methanol (Slightly)
• Water Solubility: Not miscible or difficult to mix in water. Soluble in alcohol, ether, acetone and benzene.
• Sensitive: Moisture & Light Sensitive
• Stability: Light Sensitive, Moisture Sensitive
• BRN: 1719692
• CAS DataBase Reference: cis-1,4-Dichloro-2-butene(CAS DataBase Reference)
• NIST Chemistry Reference: cis-1,4-Dichloro-2-butene(1476-11-5)
• EPA Substance Registry System: cis-1,4-Dichloro-2-butene(1476-11-5)

Safety Data

• Hazard Codes: T+,N
• Statements: 45-24/25-26-34-50/53
• Safety Statements: 53-26-28-36/37/39-45-60-61
• RIDADR: UN 3390 6.1/PG 1
• WGK Germany: 3
• RTECS: EM4900000
• F: 8-21
• TSCA: Yes
• HazardClass: 8
• PackingGroup: I
• Hazardous Substances Data: 1476-11-5(Hazardous Substances Data)

Usage

Chemical Properties

Light-Yellow Clear Liquid

Uses

It is employed as an intermediate for the production of other chemicals such as in the production of chloroprene. It is also used as a starting material in the production of adiponitrile, butane-1,4-diol, and tetrahydrofuran. It is also used in the preparation of functionalized 3,5-disubstituted cyclopent-2-enones.

InChI:InChI=1/C4H6Cl2/c5-3-1-2-4-6/h1-2H,3-4H2/b2-1-

Synthetic route

1,4-butenediol (6117-80-2) → Z-1,4-dichlorobutene (1476-11-5)

Conditions	Yield
With 1,2,3-Benzotriazole; thionyl chloride In dichloromethane at 20℃; Substitution;	94%
With thionyl chloride at 20℃; for 16h; Cooling with ice;	84%
With thionyl chloride at 20℃; for 16.66h; Cooling with ice; Inert atmosphere;	84%

(Z)-but-2-ene-1,4-diyl dimethanesulfonate (1953-56-6, 70886-56-5, 2303-47-1) → Z-1,4-dichlorobutene (1476-11-5)

Conditions	Yield
With calcium chloride In dimethyl sulfoxide for 3h; Ambient temperature;	60%

2,5-dihydrofuran (1708-29-8) → Z-1,4-dichlorobutene (1476-11-5)

Conditions	Yield
With thionyl chloride; zinc(II) chloride at 80 - 85℃;
With hydrogenchloride at 90℃; for 4h;	4.2 g

buta-1,3-diene (106-99-0) → Z-1,4-dichlorobutene (1476-11-5) + trans-1,4-dichlorobut-2-ene (110-57-6) + 3,4-dichlorobut-1-ene (310447-99-5, 310448-01-2)

Conditions	Yield
With iodine; copper dichloride In benzene at 70℃; for 2h;
With copper dichloride In acetonitrile at 60℃; for 2h;

trans-1,4-dichlorobut-2-ene (110-57-6) → Z-1,4-dichlorobutene (1476-11-5)

Conditions	Yield
at 99.9℃; Kinetics; Thermodynamic data; Equilibrium constant; activation parameters;

1,4-Dichloro-2-butyne (821-10-3) + cyclohexene (110-83-8) → Z-1,4-dichlorobutene (1476-11-5)

Conditions	Yield
With borane; acetic acid Product distribution; multistep reaction, stereospecificity, various alkenes;

3,4-dichlorobut-1-ene (310447-99-5, 310448-01-2) → Z-1,4-dichlorobutene (1476-11-5) + trans-1,4-dichlorobut-2-ene (110-57-6)

Conditions	Yield
With poly(p-xylylene); palladium In toluene at 99.85℃; Product distribution;
With oxygen at 100℃;

2,5-dihydrofuran (1708-29-8) + thionyl chloride (7719-09-7) + (E)-3-Ureido-but-2-enoic acid ethyl ester (5435-44-9, 22243-66-9) → Z-1,4-dichlorobutene (1476-11-5)

hydrogenchloride (7647-01-0) + 1,4-butenediol (6117-80-2) → Z-1,4-dichlorobutene (1476-11-5) + cis-4-chloro-buten-(2)-ol-(1)

Conditions	Yield
at 40℃;

Z-1,4-dichlorobutene (1476-11-5) + hexamethylenetetramine (100-97-0) → 1-<(Z)-4-Chloro-2-butenyl>-1-azonia-3,5,7-triazatricyclo<3.3.1.1.3,7>decane chloride (117175-09-4)

Conditions	Yield
In dichloromethane for 5h; Reflux; Large scale reaction;	100%
In ethanol; chloroform for 4h; Heating;	99%
In chloroform at 60℃; for 4h;	94%
In chloroform for 4h; Heating;	91%
In chloroform for 4h; Reflux;	91%

Z-1,4-dichlorobutene (1476-11-5) + sodium methanetricarboxylic acid triethyl ester → triethyl 5-chloro-cis-pent-3-ene-1,1,1-tricarboxylate (262863-53-6)

Conditions	Yield
In N,N-dimethyl-formamide; toluene at 80℃; Alkylation;	100%

Z-1,4-dichlorobutene (1476-11-5) → 1-(benzenesulfonyl)-2,5-dihydro-1H-pyrrole (16851-71-1)

Conditions	Yield
Stage #1: benzenesulfonamide With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.166667h; Stage #2: Z-1,4-dichlorobutene In N,N-dimethyl-formamide at 20℃; for 20h;	100%

Z-1,4-dichlorobutene (1476-11-5) + phenylsulfenyl bromide (28074-23-9) → (2-Bromo-3-chloro-1-chloromethyl-propylsulfanyl)-benzene (85335-83-7)

Conditions	Yield
In dichloromethane for 9h; Ambient temperature;	99%

Z-1,4-dichlorobutene (1476-11-5) + malonic acid dimethyl ester (108-59-8) → Dimethyl 3-cyclopentene-1,1-dicarboxylate (84646-68-4)

Conditions	Yield
Stage #1: malonic acid dimethyl ester With lithium hydride In N,N-dimethyl-formamide at 0℃; for 4h; Stage #2: Z-1,4-dichlorobutene In N,N-dimethyl-formamide at 0 - 20℃;	99%
Stage #1: malonic acid dimethyl ester With lithium hydride In N,N-dimethyl-formamide at 0℃; for 2h; Inert atmosphere; Stage #2: Z-1,4-dichlorobutene In N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere;	87%
Stage #1: malonic acid dimethyl ester With lithium hydride In N,N-dimethyl-formamide at 0℃; for 2h; Stage #2: Z-1,4-dichlorobutene In N,N-dimethyl-formamide at 0 - 25℃; for 72h;	84%

Z-1,4-dichlorobutene (1476-11-5) + N1,N4-bis(mesitylenesulfonyl)-N4-ethyl-1,4-diaminobutane (189341-51-3) → N3,N8-bis(mesitylenesulfonyl)-12-chloro-3,8-diaza-(10Z)-dodecane (304862-53-1)

Conditions	Yield
Stage #1: N1,N4-bis(mesitylenesulfonyl)-N4-ethyl-1,4-diaminobutane With sodium hydride In N,N-dimethyl-formamide at 20℃; for 2h; Stage #2: Z-1,4-dichlorobutene In N,N-dimethyl-formamide at 50℃; for 18h; Further stages.;	99%

Z-1,4-dichlorobutene (1476-11-5) + phenol (108-95-2) → (Z)-1,4-di(phenoxy)but-2-ene (52752-55-3)

Conditions	Yield
Stage #1: phenol With potassium hydroxide In ethanol for 0.5h; Schlenk technique; Inert atmosphere; Reflux; Stage #2: Z-1,4-dichlorobutene In ethanol at 0 - 20℃; Schlenk technique; Inert atmosphere; Reflux;	98%
Stage #1: phenol With potassium hydroxide In ethanol for 0.25h; Heating; Stage #2: Z-1,4-dichlorobutene at 20℃; for 15h;	75%
(i) NaOH, MeOH, (ii) /BRN= 1719692/; Multistep reaction;

Z-1,4-dichlorobutene (1476-11-5) + (2R)-2,5-dihydro-2-isopropyl-3,6-dimethoxypyrazine (109838-85-9) → (Z)-1,4-bis((2S,5R)-5-isopropyl-3,6-dimethoxy-2,5-dihydropyrazin-2-yl)but-2-ene (159344-53-3)

Conditions	Yield
Stage #1: (2R)-2,5-dihydro-2-isopropyl-3,6-dimethoxypyrazine With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #2: Z-1,4-dichlorobutene In tetrahydrofuran at 20℃; for 10h; Inert atmosphere;	97.5%

Z-1,4-dichlorobutene (1476-11-5) + N1,N4-bis(mesitylenesulfonyl)-N4-ethyl-1,4-diamino-2-butene (304862-42-8) → N3,N8-bis(mesitylenesulfonyl)-12-chloro-3,8-diaza-(5Z,10Z)-dodecadiene (304862-46-2)

Conditions	Yield
Stage #1: N1,N4-bis(mesitylenesulfonyl)-N4-ethyl-1,4-diamino-2-butene With sodium hydride In N,N-dimethyl-formamide at 20℃; for 2h; Stage #2: Z-1,4-dichlorobutene In N,N-dimethyl-formamide at 50℃; for 18h; Further stages.;	97%

Z-1,4-dichlorobutene (1476-11-5) + N,N'-(1,2-phenylene)bis(4-methoxybenzenesulfonamide) (220166-48-3) → C24H24N2O6S2

Conditions	Yield
With potassium carbonate In acetonitrile for 24h; Reflux;	97%

Z-1,4-dichlorobutene (1476-11-5) + bis(phenylsulfonyl)methane (3406-02-8) → 1,1-bis(phenylsulfonyl)-3-cyclopentene (110890-37-4)

Conditions	Yield
With sodium hydroxide; tetrabutyl ammonium fluoride In toluene for 20h; Ambient temperature;	96%

Z-1,4-dichlorobutene (1476-11-5) + 2-hydroxy-1-naphthoic acid sodium salt → (2Z)-4-chloro-2-butenyl 2-hydroxy-1-naphthoate (148859-57-8)

Conditions	Yield
In N,N-dimethyl-formamide at 25℃; for 17h;	95%

Z-1,4-dichlorobutene (1476-11-5) + trimethylamine (75-50-3) → cis-1-chloro-4-methylammonio-2-butene chloride

Conditions	Yield
In tetrahydrofuran for 24h; Ambient temperature;	95%

4-nitro-phenol (100-02-7) + Z-1,4-dichlorobutene (1476-11-5) → (Z)-1,4-bis(4-nitrophenoxy)but-2-ene (6892-53-1)

Conditions	Yield
Stage #1: 4-nitro-phenol With potassium hydroxide; 18-crown-6 ether In acetone for 0.25h; Heating; Stage #2: Z-1,4-dichlorobutene for 24h; Heating;	95%

bis{1,2-bis(methylphosphino)ethane}palladium(II) dichloride + Z-1,4-dichlorobutene (1476-11-5) → (1,6,9,14-tetramethyl-1,6,9,14-tetraphosphacyclohexadeca-3,11-diene)palladium dichloride

Conditions	Yield
With potassium carbonate In ethanol (under Ar); addn. of K2CO3 and the dihalogenide to a soln. of the Pd complex in EtOH, stirring at room temp. for 12 h; filtn., washing the ppt. with EtOH, evapn. of the solvent under vac. at 40°C, recrystn. from EtOH at -20°C;	95%

Z-1,4-dichlorobutene (1476-11-5) + (11aS)-8-hydroxy-7-methoxy-1,2,3,11a-tetrahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one (81307-24-6, 123355-42-0) → (11aS)-8-[(Z)-4-chloro-but-2-enyloxy]-7-methoxy-1,2,3,11a-tetrahydro-10H-pyrrolo[2,1-c][1,4]benzodiazepine-5-one

Conditions	Yield
Stage #1: (11aS)-8-hydroxy-7-methoxy-1,2,3,11a-tetrahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one With potassium carbonate In butanone for 0.5h; Stage #2: Z-1,4-dichlorobutene In butanone for 4h; Reflux;	95%

Z-1,4-dichlorobutene (1476-11-5) + 4-cyanomethyl-2-cyclopentyloxy-1-methoxybenzene (141333-36-0) → 1-[3-(cyclopentyloxy)-4-methoxyphenyl]cyclopen-3-ene-1-carbonitrile (401518-81-8)

Conditions	Yield
Stage #1: 4-cyanomethyl-2-cyclopentyloxy-1-methoxybenzene With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 1h; Stage #2: Z-1,4-dichlorobutene In tetrahydrofuran at -78℃; for 1.5h;	94%
With lithium hexamethyldisilazane In tetrahydrofuran at -78℃;	73%

styrene (292638-84-7) + Z-1,4-dichlorobutene (1476-11-5) → cinnamyl chloride (2687-12-9)

Conditions	Yield
tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride In dichloromethane for 12h; Heating;	93%

Z-1,4-dichlorobutene (1476-11-5) + 2-(3-(benzyloxy)-4-methoxyphenyl)acetonitrile (1699-39-4) → 1-(3-benzyloxy-4-methoxyphenyl)cyclopen-3-ene-1-carbonitrile (763109-95-1)

Conditions	Yield
Stage #1: 2-(3-(benzyloxy)-4-methoxyphenyl)acetonitrile With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 1h; Stage #2: Z-1,4-dichlorobutene In tetrahydrofuran at -78℃; for 1.5h;	93%

Z-1,4-dichlorobutene (1476-11-5) + trifluoromethyl hypochlorite (22082-78-6) → 1,2,4-Trichloro-3-trifluoromethoxy-butane (84011-34-7)

Conditions	Yield
In trichlorofluoromethane at -111 - 22℃; for 20h;	92%

Z-1,4-dichlorobutene (1476-11-5) + dimethyl 2-oxocyclopentane-1,3-dicarboxylate (155191-86-9) → 9-Oxobicyclo[4.2.1]non-3-ene-1,6-dicarboxylic dimethyl ester

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 70℃; for 24h;	92%

3-methylbenzyl cyanide (2947-60-6) + Z-1,4-dichlorobutene (1476-11-5) → 1-m-tolyl-cyclopent-3-enecarbonitrile (858422-91-0)

Conditions	Yield
Stage #1: 3-methylbenzyl cyanide With sodium t-butanolate In tetrahydrofuran; 1-methyl-pyrrolidin-2-one at 0℃; for 0.5h; Inert atmosphere; Stage #2: Z-1,4-dichlorobutene In tetrahydrofuran; 1-methyl-pyrrolidin-2-one at 0 - 20℃; for 3h; Inert atmosphere;	92%

Z-1,4-dichlorobutene (1476-11-5) + lead pentafluorothiophenolate (21459-27-8) → C16H6F10S2

Conditions	Yield
In toluene at 110℃; for 48h; Substitution;	91%

Z-1,4-dichlorobutene (1476-11-5) + 3-bromo-6-methylindolo<2,3-a>pyrrolo<3,4-c>carbazole-5,7-(6H)dione (172950-95-7) → 3-bromo-6-methyl-12,13-(but-2-en-1,4-yl)-12,13-dihydro-5,7-dioxo-6H-indolo[2,3-a]pyrrolo[3,4-c]carbazole

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 60℃; for 18h;	91%

Z-1,4-dichlorobutene (1476-11-5) + 2-(2-bromophenyl)acetonitrile (19472-74-3) → 1-(2-bromophenyl)cyclopent-3-ene-1-carbonitrile

Conditions	Yield
With 1-methyl-pyrrolidin-2-one; sodium t-butanolate In tetrahydrofuran at -10 - 20℃;	91%

Z-1,4-dichlorobutene (1476-11-5) + N-carboethoxyaniline (101-99-5) → ((Z)-4-Chloro-but-2-enyl)-phenyl-carbamic acid ethyl ester

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 40℃; for 5h;	90%

Z-1,4-dichlorobutene (1476-11-5) + ethyl N-(o-tolyl)carbamate (5255-71-0) → ((Z)-4-Chloro-but-2-enyl)-o-tolyl-carbamic acid ethyl ester

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 40℃; for 5h;	90%

Z-1,4-dichlorobutene (1476-11-5) + carbamic acid, (3-methyphenyl)-, ethyl ester (6135-33-7) → ((Z)-4-Chloro-but-2-enyl)-m-tolyl-carbamic acid ethyl ester

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 40℃; for 5h;	90%

Z-1,4-dichlorobutene (1476-11-5) + [4-(3-Methyl-benzyloxy)-phenyl]-carbamic acid ethyl ester (128886-43-1) → ((Z)-4-Chloro-but-2-enyl)-[4-(3-methyl-benzyloxy)-phenyl]-carbamic acid ethyl ester

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 40℃; for 5h;	90%

Upstream product

• 1708-29-8 2,5-dihydrofuran 
• 6117-80-2 1,4-butenediol 
• 106-99-0 buta-1,3-diene 
• 110-57-6 trans-1,4-dichlorobut-2-ene 
• 1953-56-6 (Z)-but-2-ene-1,4-diyl dimethanesulfonate 
• 821-10-3 1,4-Dichloro-2-butyne 
• 110-83-8 cyclohexene 
• 310447-99-5 3,4-dichlorobut-1-ene 
• 7719-09-7 thionyl chloride 
• 5435-44-9 (E)-3-Ureido-but-2-enoic acid ethyl ester 
• 7647-01-0 hydrogenchloride 

Downstream Products

• 98589-20-9 optically inactive 1,2,3,4,7-pentachloro-5,6-bis-chloromethyl-norborn-2-ene 
• 68972-96-3 (Z)-1,4-dibenzyloxy-2-butene 
• 24233-06-5 1,4-bis-cyclohexyloxy-but-2c-ene 
• 18715-38-3 trans-1,4-dicyano-2-butene 
• 33626-80-1 ethyl 1-acetylcyclopent-3-ene-1-carboxylate 
• 33626-79-8 1-acetyl-2-vinylcyclopropanecarboxylic acid ethyl ester 
• 24430-29-3 Spiro<4.4>nona-1,3,7-trien 
• 36715-51-2 (E)-1-(phenylthio)buta-1,3-diene 
• 71831-17-9 cis-1,4-diacetylthio-2-butene 
• 88326-51-6 Dimethyl 3-cyclopentene-1,1-dicarboxylate 
• 52752-55-3 (Z)-1,4-di(phenoxy)but-2-ene 
• 122535-72-2 1-(1,3-butadienyl)-1,2,4-triazole 
• 104446-06-2 3-Furan-2-yl-3-oxo-2-[3-phenyl-4-vinyl-thiazolidin-(2E)-ylidene]-propionitrile 
• 110425-66-6 (Z)-N-(4-chlorobut-2-enyl)-4-phenylazetidin-2-one 

Relevant articles and documents

Skipped cyclic ene- and dienediynes. 1. Synthesis, spectroscopic properties, and reactions of a new hydrocarbon ring family

The three skipped cyclic C12H12 dienediynes, 4,9-dimethylene-1,6-cyclodecadiyne (1), (Z,Z)-4,10-cyclododecadiene-1,7-diyne (2), and 10-methylene-(Z)-4-cycloundecene-1,7-diyne (3), have been synthesized by cyclization of dilithium salts of diterminal enediynes with the corresponding dihalogenides. This simple approach only worked (with approx. 5% yield) when no CuCl catalyst was used. Besides 1-3, 4,9-diisopropylidene-1,6-cyclodecadiyne (30), the cyclic enediynes (Z)-4-cycloundecene-1,7-diyne (19) and (Z)-4-cyclododecene-1,7-diyne (20), as well as 4-methylene-1,6-cyclodecadiyne (22), 4-methylene-1,6-cycloundecadiyne (23), and their isopropylidene congeners 25 and 28 have been synthesized. Partial hydrogenation of 1-3 gives the corresponding homoconjugated tetraenes 37-39. The reaction of 30 with dicarbonyl(η5-cyclopentadienyl)cobalt yields a superphane of two cyclobutadiene units, stabilized by two CpCo moieties (47). The two cyclobutadiene rings are connected by four 2-isopropylidenepropano bridges. An X-ray investigation of the superphane shows that all four bridges adopt a pinwheel-like conformation.

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Practical synthetic process for enantiopure 1-benzyl-3-hydroxypyrrolidine

The synthesis of (S)-1-benzyl-3-hydroxypyrrolidine (S)-5 comprised the asymmetric hydroboration of 1-benzyl-3-pyrroline 4, followed by oxidation and chiral purification via diastereomeric salt formation. The asymmetric borane reagent was generated 'in situ' from NaBH4, BF3-OEt2, and (+)-α-pinene 1 (85% ee) and reacted with 4, prepared from cis-1,4-butenediol 3, to give crude product (S)-5. The following chiral purification via diastereomeric salt formation proceeded to afford (S)-5 with >99% ee. The optimized process was successfully scaled up to an industrial scale to produce a 252 kg batch of (S)-5.