Chlorides allyl

Synonyms Chlorallylene 3-chloropropene 3-chloroprene l-chloro-2-propene 3-chloro-propylene 2-propenyl chloride 

Manufacture of epichlorohydrin, epoxy resin, glycerin pesticides, and sodium allyl sulfonate 

Toxicology. Allyl chloride is an irritant of the eyes, mucous membranes, and skin chronic exposure may cause toxic polyneuropathy. In animals it causes renal, hepatic, and pulmonary damage and, at high concentrations, central nervous system depression. 

The most frequent effects in humans from overexposure have been conjunctival irritation and eye pain with photophobia eye irritation occurs at levels between 50 and 100ppm. Irritation of the nose occurs at levels below 25 ppm. 

The liquid is a skin irritant and may be absorbed through the skin, causing deep-seated pain. If splashed in the eye, severe irritation would be expected. 

The dkect high temperature chlorination of propylene continues to be the primary route for the commercial production of aHyl chloride. The reaction results in aHyl chloride selectivities of 75—80% from propylene and about 75% from chlorine. Additionally, a significant by-product of this reaction, 1,3-dichloropropene, finds commercial use as an effective nematocide when used in soil fumigation. Overall efficiency of propylene and chlorine use thus is significantly increased. Remaining by-products include 1,2-dichloropropane, 2-chloropropene, and 2-chloropropane. 

A second method for synthesis of aHyl chloride is thermal dehydrochlorination, ie, cracking, of 1,2-dichloropropane, but this method is generally less satisfactory because of low aHyl chloride selectivity (50—60%) and operating temperatures of 500—600°C (4,7—10). The by-products of cracking are 1-chloropropene and 2-chloropropene, which have no significant commercial use. 

The oxychl orin a tion of propylene to aHyl chloride, using hydrogen chloride and oxygen, has also been demonstrated. However, with inferior yields, less than satisfactory catalyst life, and a complex processing scheme, (11—20) this route to aHyl chloride is not utilized commercially. 

AHyl chloride is a colorless Hquid with a disagreeable, pungent odor. Although miscible in typical compounds such as alcohol, chloroform, ether, acetone, benzene, carbon tetrachloride, heptane, toluene, and acetone, aHyl chloride is only slightly soluble in water (21—23). Other physical properties are given in Table 1. 

AHyl chloride exhibits reactivity as an olefin and as an organic haHde. Its activity as a chloride is enhanced by the presence of the double bond, but its activity as an olefin is somewhat less than that of propylene. AHyl chloride participates in most types of reactions characteristic of either functional group  

Data were last reviewed in lARC (1985) and the compound was classified in LARC Monographs Supplement 7 (1987). 

107-05-1 Chem. Abstr. Name 3-Chloro-l-propene lUPAC Systematic Name 3-Chloropropene Synonyms 3-Chloropropylene 2-propenyl chloride 

2 Structural and molecular formulae and relative molecular mass 

Description Colourless to pale yellow liquid with an unpleasant pungent odour (Budavari, 1996) 

Solubility Slightly soluble in water (0.36 g/100 g at 2()°C) miscible with ethanol, diethyl ether, chloroform and petroleum ether (American Conference of Governmental Industrial Hygienists, 1991 Budavari, 1996) 

---

Allyl Chloride. Comparatively poor yields are obtained by the zinc chloride - hydrochloric acid method, but the following procedure, which employs cuprous chloride as a catalyst, gives a yield of over 90 per cent. Place 100 ml. of allyl alcohol (Section 111,140), 150 ml. of concentrated hydrochloric acid and 2 g. of freshly prepared cuprous chloride (Section II,50,i one tenth scale) in a 750 ml. round-bottomed flask equipped with a reflux condenser. Cool the flask in ice and add 50 ml. of concen trated sulphuric acid dropwise through the condenser with frequent shaking of the flask. A little hydrogen chloride may be evolved towards the end of the reaction. Allow the turbid liquid to stand for 30 minutes in order to complete the separation of the allyl chloride. Remove the upper layer, wash it with twice its volume of water, and dry over anhydrous calcium chloride. Distil the allyl chloride passes over at 46-47°. 

Aside of benzene the chemist has a choice in which allyl she can use. Allyl alcohol, allyl bromide or allyl chloride can be used with equal success but allyl alcohol is a nice bonus because it is easier... 

This is similar to the Friedel-Crafts method but is less harsh and has been proven successful at producing safrole. In a very small flask is added 7.2g of allyl chloride, 34.3g 1,3-benzodioxole and 0.15g powdered Cu (which can be made by... 

The intermediate 190 of the intramolecular aminopalladation of an allenic bond with jV-tosylcarbamate undergoes insertion of allylic chloride. Subsequent elimination of PdCl2 occurs to afford the 1,4-diene system 191. The regeneration of Pd(II) species makes the reaction catalytic without using a reoxidant[190]. 

Benzoic acid and naphthoic acid are formed by the oxidative carbonylation by use of Pd(OAc)2 in AcOH. t-Bu02H and allyl chloride are used as reoxidants. Addition of phenanthroline gives a favorable effect[360], Furan and thiophene are also carbonylated selectively at the 2-position[361,362]. fndole-3-carboxylic acid is prepared by the carboxylation of 1-acetylindole using Pd(OAc)2 and peroxodisulfate (Na2S208)[362aj. Benzoic acid derivatives are obtained by the reaction of benzene derivatives with sodium palladium mal-onate in refluxing AcOH[363]. 

Aldehydes can also be prepared by the carbonylation of aryl and alkenyl halides and triflate, and benzyl and allyl chlorides using tin hydride as a hydride source and Pd(PhjP)4 as a catalyst[377]. Hydrosilancs arc used as another hydride source[378]. The arenediazonium tetralluoroborate 515 is converted into a benzaldehyde derivative rapidly in a good yield by using Et ,SiH or PH MS as the hydride source[379]. 

The allyl-substituted cyclopentadiene 122 was prepared by the reaction of cyclopentadiene anion with allylic acetates[83], Allyl chloride reacts with carbon nucleophiles without Pd catalyst, but sometimes Pd catalyst accelerates the reaction of allylic chlorides and gives higher selectivity. As an example, allylation of the anion of 6,6-dimethylfulvene 123 with allyl chloride proceeded regioselectively at the methyl group, yielding 124[84]. The uncatalyzed reaction was not selective. 

Ketones can be prepared by trapping (transmetallation) the acyl palladium intermediate 402 with organometallic reagents. The allylic chloride 400 is car-bonylated to give the mixed diallylic ketone 403 in the presence of allyltri-butylstannane (401) in moderate yields[256]. Alkenyl- and arylstannanes are also used for ketone synthesis from allylic chlorides[257,258]. Total syntheses of dendrolasin (404)f258] and manoalide[259] have been carried out employing this reaction. Similarly, formation of the ketone 406 takes place with the alkylzinc reagent 405[260],... 

The /3,7-unsaturated aldehyde 407 is prepared in good yields by the carbo-nylation of an allylic chloride under mild conditions using tributyltin hydride as a hydride source[261]. Aldehydes are obtained in moderate yields by the reaction of CO and H2[262],... 

Organoboranes are reactive compounds for cross-coupling[277]. The synthesis of humulene (83) by the intramolecular cross-coupling of allylic bromide with alkenylborane is an example[278]. The reaction of vinyiborane with vinyl-oxirane (425) affords the homoallylic alcohol 426 by 1,2-addition as main products and the allylic alcohol 427 by 1,4-addition as a minor product[279]. Two phenyl groups in sodium tetraphenylborate (428) are used for the coupling with allylic acetate[280] or allyl chloride[33,28l]. 

It was claimed that the Z-form of the allylic acetate 430 was retained in homoallylic ketone 431 obtained by reaction with the potassium enolate of 3-vinylcyclopentanone (429), after treatment with triethylborane[282]. Usually this is not possible. The reaction of a (Z)-allylic chloride with an alkenylaluminum reagent to give 1,4-dienes proceeds with retention of the stereochemistry to a considerable extent when it is carried out at -70 C[283]. 

Coupling of allyl chloride with the (2 -alkenylpentafluorosilicate 463 using Pd(OAc)j as a catalyst at room temperature gives a 1,4-diene in good yields. The reaction has been applied to the synthesis of recifeiolide[299]. 

Intramolecular reaction of the allenyl carbamate 5 in the presence of a large excess of allylic chloride catalyzed by Pdi(dba)3 or PdCl2(PhCN)2 affords the substituted oxazolidin-2-one 6. Since the reaction is catalyzed by both Pd(II) and Pd(0), its mechanism is not dear[3]. 

The first step of the reaction is the oxypalladation of the triple bond with PdCl2 as shown by 228 to form the alkenylpalladium species 229, and the Pd is displaced with proton to regenerate Pd(TI) species and the lactone 224. The alkenylpalladium species 229 can be utilized for further reaction. When allyl chloride (230) is added, double bond insertion is followed by elimination of... 

PdCb, and the allylated lactone 232 is formed. Regeneration ofPdCl2 as shown by 231 makes the reaction catalytic. In this reaction, use of the Li salt 227 of 4-pentynoic acid (223) is recommended. Reaction of lithium 3-octynoate (233) with allyl chloride affords the unsaturated lactone 234, which is converted into the 7-keto acid 235 by hydrolysis[126]. 

Propargylic alcohol, after lithiation, reacts with CO2 to generate the lithium carbonate 243, which undergoes oxypalladation. The reaction of allyl chloride yields the cyclic carbonate 244 and PdC. By this reaction hydroxy and allyl groups are introduced into the triple bond to give the o-allyl ketone 245[129]. Also the formation of 248 from the keto alkyne 246 with CO2 via in situ formation of the carbonate 247 is catalyzed by Pd(0)[130]. 

The cyclic enol ether 255 from the functionalized 3-alkynoI 254 was converted into the furans 256 by the reaction of allyl chloride, and 257 by elimination of MeOH[132], The alkynes 258 and 260, which have two hydroxy groups at suitable positions, are converted into the cyclic acetals 259 and 261. Carcogran and frontalin have been prepared by this reaction[124]. 

The reaction of allyl halides with terminal alkynes by use of PdClifFhCNji as a catalyst affords the l-halo-l,4-pentadienes 297. 7r-AlIylpalladium is not an intermediate in this reaction. The reaction proceeds by chloropalladation of the triple bond by PdCh, followed by the insertion of the double bond of the allyl halide to generate 296. The last step is the regeneration by elimination of PdCh, which recycles[148]. The cis addition of allyl chloride to alkynes is supported by formation of the cyclopentenone 299 from the addition product 298 by Ni(CO)4-catalyzed carbonylation[149]. 

Allylic IS often used as a general term for molecules that have a functional group at an allylic position Thus the following compounds represent an allylic alcohol and an allylic chloride respectively... 

The first order rate constant for ethanolysis of the allylic chloride 3 chloro 3 methyl 1 butene is over 100 times greater than that of tert butyl chloride at the same temperature... 

Both compounds react by an S l mechanism and their relative rates reflect their acti vation energies for carbocation formation Because the allylic chloride is more reactive we reason that it ionizes more rapidly because it forms a more stable carbocation Struc turally the two carbocations differ m that the allylic carbocation has a vinyl substituent on Its positively charged carbon m place of one of the methyl groups of tert butyl cation... 

Although alkenes typically react with chlorine and bromine by addition at room tern perature and below (Section 6 14) substitution becomes competitive at higher tempera tures especially when the concentration of the halogen is low When substitution does occur It IS highly selective for the allylic position This forms the basis of an industrial preparation of allyl chloride... 

Other sources of by-product HCl include allyl chloride, chlorobenzenes, chlorinated paraffins, linear alkylbenzene, siHcone fluids and elastomers, magnesium, fluoropolymers, chlorotoluenes, benzyl chloride, potassium sulfate, and agricultural chemicals. 

Quantitative Analysis of All llithium Initiator Solutions. Solutions of alkyUithium compounds frequentiy show turbidity associated with the formation of lithium alkoxides by oxidation reactions or lithium hydroxide by reaction with moisture. Although these species contribute to the total basicity of the solution as determined by simple acid titration, they do not react with allyhc and henzylic chlorides or ethylene dibromide rapidly in ether solvents. This difference is the basis for the double titration method of determining the amount of active carbon-bound lithium reagent in a given sample (55,56). Thus the amount of carbon-bound lithium is calculated from the difference between the total amount of base determined by acid titration and the amount of base remaining after the solution reacts with either benzyl chloride, allyl chloride, or ethylene dibromide. 

---