Examples of Synthetic Methods
1,1-Dichlorooctane (Fig. 17) and 1,1,X-trichlorooctanes (Fig. 20) 
1,115 g (5.350 mol) of phosphorus pentachloride and 500 g of benzene was placed into a 5-l., 3-neck flask. To the stirred slurry was added 600 g (4.7 mol) of octanal over a 5-h period at no more than 10°C. After standing overnight, ice and water were added slowly with cooling. The product was washed with sodium bicarbonate and water and then dried (MgSO4). The product was distilled; the fraction boiling at 95–99°C was found to be 97% pure 1,1-dichlorooctane contaminated with octanal. Since the removal of octanal by sodium bisulfite washes was not successful, the product was redistilled to give 98.6% pure material.
1,1-X-Trichlorooctanes: to a 1-l. turbomixer, with an internal cooling coil and gas inlet at the bottom, was placed 499 g (2.58 mol) of 1,1-dichlorooctane. Nitrogen was bubbled through the mixture for 30 min. Chlorine was then passed with rapid stirring at about 25°C for 1 h at 258 mL/min with a GE sun lamp to initiate the reaction. Nitrogen was then bubbled through the mixture for 1 h and the reaction mixture washed with water, twice with 10% sodium bicarbonate, and finally with water. The mixture was dried (MgSO4) and distilled. The fraction boiling at 117–130°C (15 mm) was used in the alkylation studies. The composition of this fraction was 1,1,1- (trace), 1,1,2- (2%), 1,1,3- (10.5%), 1,1,4- (16.1%), 1,1,5- (17.9%), 1,1,6- (21.0%), 1,1,7- (23.8%), and 1,1,8-trichlorooctane (10.3%).
After the alkylation reaction was complete, the 1,1,8 isomer and a mixture of the 1,1,2 and 1,1,3 isomers were trapped from a 10 ft × 0.25 in. 20% Carbowax on Chromosorb W column.
The NMR of the 1,1,8 isomer showed a triplet at 5.56 (CHCl), a triplet at 3.38 (CH2Cl), a crude quartet at 2.16 (CH2CCl2), and methylene protons at 1.37 ppm.
The mixture of 1,1,2 and 1,1,3 isomers – the latter being predominant – showed a pair of overlapping doublets at 5.8, a smaller doublet at 5.71, a complex peak at 3.96, a pair of overlapping doublets at 2.42, methylene protons at 1.3, and terminal methyl at 0.89 ppm. The mixture was then subjected to spin-spin decoupling treatment. Irradiation at 3.9 ppm (a) collapsed the 5.8 ppm band to a triplet, (b) collapsed the 5.71 ppm doublet to a singlet, thereby giving a good indication that the minor constituent was the 1,1,2 isomer, and (c) collapsed the 2.42 ppm doublet pair to one doublet. Irradiation at 2.5 ppm reduced the 5.8 ppm doublets to a singlet and the complex group at 3.96 ppm to a crude triplet. Irradiation at 5.8 ppm did not affect the 3.96 ppm group but reduced the bands at 2.42 ppm to a doublet. C-3 of the 1,1,3 isomer is asymmetric; hence the protons on C-2 are not magnetically equivalent. The assignment of the bands at 5.8 (Cl2CH), 3.96 (CHCl), and 2.42 ppm (Cl2CCH2CCl), and the behavior in the spin–spin decoupling treatment are consistent with that for the 1,1,3 isomer.
1,1,1-Trichlorooctane and 1,1,1,X-tetrachlorooctanes (Fig. 20) 
1,1,1-Trichlorooctane: Into a 1-l., stainless steel, stirred autoclave was placed 186 g (1.90 mol) of 1-heptene, 900 g (6.56 mol) of chloroform, and 4.0 g of benzoyl peroxide. The sealed bomb was heated at 80°C for 4 h and a further 8 g of benzoyl peroxide added. The bomb was then heated for another 6 h at 90°C. This procedure was repeated; the two products were combined. The unreacted chloroform and 1-heptene were removed by distillation, and the bulk of the product distilled at 84–86°C (6 mm). More careful fractionation of the 240 g of product so obtained gave a product of 98.5% purity boiling at 85°C (6 mm).
1,1,1,X-Tetrachlorooctanes: The chlorination of 1,1,1-trichlorooctane used the previously described procedure (See 5.1.1). The fraction boiling at 115–123°C (6 mm) was used in the alkylation studies. The composition of this fraction was 1,1,1,3- (3.2%), 1,1,1,4- (19.7%), 1,1,1,5- (22.9%), 1,1,1,6- and 1,1,1,7- (46.7%), and 1,1,1,8-tetrachlorooctane (6.3%). The impurities plus the 1,1,1,2 isomer constituted 1.2% of the mixture. Concentration of various isomers, either from distillation cuts before reaction or by trapping the unreactive isomers after reaction, permitted spectroscopic methods to substantiate the assignments. Further, the 1,1,1,3 isomer was synthesized by the addition of carbon tetrachloride to 1-heptene [b.p. 105–106°C (6 mm)].
The NMR of the 1,1,1,3 isomer showed peaks at 4.2 (m, CHCl), 3.18 (eight line distinctive multiplet), 1.82 (m, CClCH2), 1.4 (methylene protons), and 0.99 ppm (terminal methyl). The most distinctive feature from the NMR of the 1,1,1,6 isomer was the triplet methyl group at 1.14 ppm. The doublet methyl group of the 1,1,1,7 isomer was observed in the NMR at 1.6 ppm. The NMR of the 1,1,1,8 isomer showed a band at 3.4 ppm (t, ClCH2 ) and was distinctive because of the absence of the terminal methyl group.
1,1,5-Trichlorooctanes and 1,1,6-Trichlorooctanes, 1,1,5-Trichlorononanes and 1,1,6-Trichlorononanes, 1,1,5-Trichloroundecanes and 1,1,6-Trichloroundecanes (Fig. 43) 
A mixture of 4.35 g (20 mmole) of 1,1,1-Trichlorooctane, 9.6 g (160 mmole) of iso-C3H7OH, and 0.59 g (3 mmole) of Fe(CO)5 was heated at 120°C for 3 h. The reaction mixtures from five experiments were combined and distilled with collection of the fraction that boiled up to 80°C (iso-C3H7OH and its transformation products). The residue was washed with 10% HCI and water and distilled in vacuo to give 12.4 g (65%) of 1,1-dichlorooctane with b.p. 85–87°C (15 mm). According to GLC data the fraction with b.p. 97–128°C (10 mm) (4.2 g) contained two substances. Preparative GLC yielded 1,1,5- and 1,1,6-trichlorooctanes in the form of 95% enriched fractions containing the second isomer.
Reduction of 1,1,1-Trichlorononane in the Presence of Mn 2 (CO) 10 . A mixture of 20 mmole of 1,1,1-Trichlorononane, 160 mmole of iso-C3H7OH, and 2 mmole of Mn2(CO)10 was heated at 120°C for 3 h. The reaction mixtures from three experiments were combined and worked up to give 9.4 g (68%) of 1,1-dichlorononane with b.p. 102–104°C (15 mm). The undistilled residue (1.6 g) contained 1,1,5- and 1,1,6-trichlorononanes, which were identified by GLC with reference to samples obtained by an independent method.
Reduction of 1,1,1-Trichloroundecane in the Presence of Mo(CO) 6 . A mixture of 20 mmole of 1,1,1-Trichloroundecane, 160 mmole of iso-C3H7OH, and 1 mmole of Mo(CO)6 was heated at 140°C for 3 h. The reaction mixtures from five experiments were combined and worked up. Distillation gave 16.6 g (74%) of 1,1-dichloroundecane with b.p. 101–102°C (2 mm) and a fraction containing, according to GLC data, 3.2 g (16%) of a mixture of 1,1,5- and 1,1,6-trichloroundecanes, which were identified by GLC with reference to samples obtained by an independent method .
1,1,1,3-Tetrachlorooctane, 1,1,1,3-Tetrachlorononane, 1,1,1,3,6,8,8,8-Octachlorooctane (Fig. 30) 
All reactions and preparative manipulations were carried under nitrogen atmosphere, using Schlenck techniques. Acetonitrile was distilled from P2O5 prior to use. Propionitrile and benzonitrile, reagent grade, were used without purification. In a typical reaction, the catalyst, olefin substrate and the polyhalide, in a molar ratio of 0.05:1:6.6, were refluxed in the solvent under dry nitrogen atmosphere for the time specified; [olefin substrate] = 0.7 M.
Isolation of the product was conducted by distilling the solvent and the excess polyhalide, followed by precipitation of the catalyst (oxidized) with pet ether followed by passing the resulting clear solution through a short silica column. The crude product was then purified by vacuum distillation.
1,1,1,3-Tetrachlorononane (24h), 85%, b.p. 112 8°C/1 mmHg. 1H-NMR: δ = 0.9 (t, 3H), 1.4 (m, 8H), 1.9 (m, 2H), 3.2 (ddd, 2H), 4.2 (m, 1H). MS: m/z (%) = 223(19), 193(29), 185(35), 157(100), 149(29), 132(58), 121(94), 109(73).
1,1,1,3-Tetrachlorooctane (23h), 80%, b.p. = 54°C/0.1 mmHg. 1H-NMR: δ = 0.9 (t, 3H), 1.5 (m, 6H), 1.9 (m, 2H), 3.2 (ddd, 2H), 4.2 (m, 1H). MS: m/z (%) = 223(7), 187(11), 179(23), 143(54), 107(51), 97(43), 82(58), 69(67), 55(97), 41(100).
1,1,1,3,6,8,8,8-Octachlorooctane (22h), 22%, b.p. = 114–120°C/0.3 mmHg. 1H-NMR: δ = 1.6–2.4 (m, 4H), 3.2 (dddd, 4H), 4.3 (m, 2H). MS: m/z (%) = 317(50), 281(33), 245(50), 221(30), 183(28), 159(31), 143(55), 123(44), 109(100), 87(33), 75(58), 61(23), 43(58).
1,1,1,3,6,8,8,8-Octachlorooctane (Fig. 24) 
A mixture of biallyl (41 g., 0.5 mole), carbon tetrachloride (318 g., 2.07 moles), and acetyl peroxide (3.4 g., 0.029 mole) was heated to reflux under an excess pressure of 15 cm. of mercury. After 5 h heating, the boiling point had risen from 85°C to 96°C. In the −80°C cold trap, a small amount of methyl chloride was collected. The excess carbon tetrachloride was distilled from the reaction mixture, and the residue was fractionated under reduced pressure. A fraction boiling at 50–60°C (0.4 mm.) was collected. Upon distillation this material yielded 31g. of tetrachloroheptene; b.p. 57–59°C (0.4 mm.).
The residual portion of the reaction mixture (85 g.) was distilled in a molecular still. Successive portions of the distillate (60 g.) showed a progressively decreasing chlorine content: from 69.2 to 63.8%. On standing, fine white needles were formed by partial crystallization of the distillate. These were washed quickly with a little methyl alcohol and dried. This material (m. p. 72–74°C) appeared to be octachlorooctane.
1,1-Dichlorononane (Fig. 42) 
The reaction product from 1,1,1-Trichlorononane (10.2 g, 50 mmol) was distilled in vacuum. Three fractions were obtained: (1) b.p. 77–80°C (10 mm) 2.5 g; (2) b.p. 62–70°C (1 mm) 2.4 g; (3) b.p. 78–80°C (1 mm) 5 g.
1,1-Dichlorononane was isolated from fraction 1 by a repeated distillation and had b.p. 59°C (2 mm). 13C NMR spectrum (δ, ppm): 73.5 (C-1), 44.0 (C-2), 28.8 (C-3), 26.2 (C-4), 29.6 (C-5), 29.4 (C-6), 32.1 (C-7), 22.8 (C-8), 14.1 (C-9).
2,2-Dichlorononane (Fig. 17, Reaction 2) 
Chlorine was bubbled by stirring in dichloromethane (40 mL) containing 2-nonanone oxime (2 g) and aluminum trichloride (1 g). The mixture was poured over ice (100 g) and then extracted with ether (100 mL). The organic layer was washed with 5% hydrochloric acid, sodium hydrogen carbonate solution, and brine and then dried over magnesium sulfate. 2,2-Dichlorononane: yield 82%, b.p. = 59°C (30.8 Torr), 1H NMR 2.05 ppm (COCH2), 2.1 ppm (CH3). 13C NMR 37.2(C-1), 90.6(C-2), 49.7(C-3), 25.6 (C-4), 28.8–28.4(C-5, C-6), 31.6(C-7), 22.6(C-8), 13.9(C-9).
1,1,1-Trichlorononane, A (Fig. 37) 
The radical telomerization of 20 g of 1-octene (0.178 mol) and 213 g of chloroform (1.78 mol) was initiated by 0.71 g of di(p-tert-butylcyclohexyl)percarbonate (1.78 mmol). The reaction was performed under argon at 60°C for 10 h. A colorless oil was distilled: CCl3CH2(CH2)6CH3, (yield 52%; b.p. = 50°C/2 mm Hg). 1H-NMR (CDCl3): δ = 0.9 (t; 3H; CH3), 1.3 (m; 10H; C5 H 10CH3), 1.8 (m; 2H; CCl3CH2CH 2), 2.65 (2H; m; CCl3CH2). 13C-NMR (dmf-d 7): δ = 14.4 (CH3, 1C), 23.1–32.5 (C 6H12CH3, 6C), 55.4 (CCl3 CH2, 1C), 101.3 (CCl3, 1C).
1,1,1-Trichlorononane, B (Fig. 23) 
Octene-1 (28 g., 0.25 mole), chloroform (120 g., 1 mole), and benzoyl peroxide (0.5 g.) were mixed and heated under 20 cm excess pressure for ten hours during which time the boiling point of the mixture rose from 80 to 92°C. After 4 h, an additional amount of benzoyl peroxide (1.0 g., total 0.006 mole) was added. On distillation of the reaction mixture, about 1.5 g. of unchanged octene was recovered; on further distillation, a fraction boiling at 65–75′ (0.1 mm.) was obtained. When redistilled, this material gave a product which was shown to be 1,1,1-trichlorononane, 13 g. (22%); b.p. 65–70°C (0.5 mm.).
1,1,9-Trichlorononane, A (Fig. 42) 
1,1,1,9-Tetrachlorononane was reduced with a system consisting of Fe(CO)5 (15 mole %) and HMPA (100 mole %) at 140°C for 3 h in a stream of nitrogen. The reaction mixture was processed, distilled, and from the fraction of b.p. 78–80°C (10 mm) containing 95% of 1,1,9-trichlorononane and 5% 1,1,1,9-tetrachlorononane, 1,1,9-trichlorononane was isolated by preparative GLC.
13C NMR spectrum (δ, ppm): 73.7 (C-1), 43.7 (C-2), 25.9 (C-3), 29.3 (C-4), 28.8 (C-5), 28.5 (C-6), 26.9 (C-7), 32.7 (C-8), 44.8 (C-9).
1,1,9-Trichlorononane, B (Fig. 41) 
A solution of 0.77 g of Fe(CO)5 in 20 g of n-C4H9SH was added with stirring to 22 g of 1,1,1,7-tetrachloroheptane heated to 145°C at such a rate that the temperature in the reaction mixture was 140–145°C. The HCl liberated was collected in water, and was determined quantitatively by the titration of an aliquot part with 0.1 N NaOH solution at the end of the reaction.
The yield of HCl was 73% of theoretical. The di-n-butyl disulfide formed was isolated from the reaction mixture by distillation through a column with a yield of 83% of theoretical. By distillation from a Favorskii flask, the residue yielded 14.1 g (75%) of 1,1,7-trichloroheptane contaminated with a small amount of dibutyl disulfide. After redistillation, the 1,1,7-trichloroheptane was obtained in the pure state according to the results of GLC and analysis.
1,1,9-trichlorononane was obtained similarly; 71%, b.p. 123°C (3 mm Hg).
1,3,3-Trichlorononane and 1,3,3,5-Tetrachlorononane (Fig. 25) 
Reaction of 1,1,1,3-Tetrachloropropane with 1-Hexene.
All the experiments were run and worked up by the general procedure described in . Fractional distillation of the reaction mixture from the experiment run at 105°C in the presence of hexamethylphosphotriamide + N,N-dichloro-p-chlorobenzenesulfonamide gave 22.5 mmoles of 1,3,3,5-tetrachlorononane, b.p. 126°C (3m m), PMR spectrum (δ, ppm): 0.70–2.07m (C4H9, 9H), 2.72m (4H, 2CH2), 3.82t (2H, CH2Cl), 4.25m (1H, CHCl).
From the reaction mixture by preparative GLC we isolated 1,3,3-trichlorononane, b.p. 85–88°C (1 mm); PMR spectrum (δ, ppm): 0.65–1.90m (11H, C5H11), 2.17m (2H, CH2), 2.60t (2H, CH2CCl2), 3.84t (2H, CH2Cl).
2,2,4-Trichlorononane and 2,2-dichlorononane (Fig. 25) 
A mixture of 5 g olefin, 33.4 g of 1,1,1-Trichloroethane, 17 g of HSiEt3, and 1.5 g of tert-butylperoxide (TBP) was heated at 130–140°C. Gas–liquid chromatographic analysis of the reaction products indicated the formation of 3.3 g (33%) 2,2-dichlorononane and 1.2 g (10%) 2,2,4-trichlorononane. The mixture was fractionated after washing with dilute hydrochloric acid, water, extraction, and drying. The fraction with b.p. 106–111°C (16 mm) (7.6 g) was subjected to preparative gas–liquid chromatography to give 2,2-dichlorononane. PMR spectrum (δ, ppm): 0.84 m, 1.2 m (CH3, 6CH2, 15H), 2.0 s (CH3CCl2, 3H).
The fraction with b.p. 112–116°C (16 mm) (4.6 g) was subjected to chromatography to yield 2,2,4-trichlorononane. PMR spectrum (δ, ppm), 2.18 s (CH3CCl2, 3H), 2.6 d (CCl2CH2, 2H), 4.0 m (CHCl, 1H), and 0.94 m and 0.9 m (4CH2, CH3, 11H).
3,3,5-Trichlorononane (Fig. 25) 
A mixture of 0.39 M of CCl3C2H5, 0.33 M of 1-hexene, 0.78 M of iso-C3H7OH, (abs.), and 6 mM of Fe(CO)5 was heated for 5 h in an autoclave at 135°C. After distilling off fraction I, 47.8 g, b.p. 36–86°C, and washing out the iron salts, fraction II was obtained by distillation with b.p. 67–84°C (2 mm), 32.4 g, and a residue of 9.5 g which was not investigated. From the GLC results, fraction II contained 0.061 M of CH3CH=CClCH2CHClC4H9 and 0.082 M of C2H5CCl2CH2–CHClC4H9.
By repeated distillation of fraction II we isolated 9 g of 3,5-Dichloro-2-nonene (11.8% of theor.) From fraction II we isolated 16.9 g (18.8%) of 3,3,5-Trichlorononane.
1,1,1,3-Tetrachlorononane (Fig. 23) and 7,9,9,11-tetrachloroheptadecane 
Reaction of Carbon Tetrachloride with Octene-1: Octene-1 (b.p. 121.2°C (750 mm.); (37 g., 0.33 mole), carbon tetrachloride (154 g., 1.0 mole) and benzoyl peroxide (5 g., 0.02 mole) were heated together under an excess pressure of 15 cm. of mercury. Carbon dioxide was steadily evolved for about 4 h, during which time the boiling point of the reaction mixture rose from 90 to 105°C. The excess of carbon tetrachloride was then removed by distillation, and the residue was distilled in vacuo. The forerun contained a small amount of a white solid material. A fraction (72 g) boiling at 75–85°C (0.05 mm.) was collected and redistilled. The yield of redistilled product was 66 g. (75%); b.p. 78–79°C (0.1 mm.). This material was 1,1,1,3-tetrachlorononane.
The residue (12.5 g.) was distilled in a molecular still. Three fractions were taken; these showed a progressive decrease in chlorine content from 46.8 to 41.0%. A compound consisting of two moles of octene and one mole of carbon tetrachloride contains 37.6% chlorine. Therefore, the high-boiling material is probably a mixture of C9H16Cl4 and C17H32C14.
When acetyl peroxide instead of benzoyl peroxide was used to initiate the reaction of carbon tetrachloride with octene-1, the results were similar. The yield of 1,1,1,3-tetrachlorononane obtained was 85% of the calculated amount.
The Reaction of Carbon Tetrachloride with Octene-1 in Ultraviolet Light: Carbon tetrachloride (182.1 g., 1.18 mole) and octene-1 (39.9 g., 0.36 mole) were mixed in a quartz reflux apparatus. The mixture was held at its boiling point and irradiated with a 500-watt ultraviolet lamp for a period of 4 h. After the unchanged carbon tetrachloride and octene-1 had been removed by distillation, 1,1,1,3-tetrachlorononane (b.p. 72–75°C (0.1 mm.) distilled. A residue (3.9 g.) remained in the distilling flask.
1,1,1,9-Tetrachlorononane (Fig. 36) 
A stainless steel-lined tubular pressure reactor having an internal volume of about 350 mL and equipped with a thermocouple well and gas inlet was charged with 210 g. (1.36 moles) of freshly distilled carbon tetrachloride, 35 g. of water, and 0.47 g. (0.00194 mole) of benzoyl peroxide (“Lucidol”). The reactor was evacuated, pressured to 500 lb./sq. in. with ethylene, and placed horizontally in a shaking box equipped with a heater. When the temperature of the reaction mixture was raised to 70°, the pressure was increased to 1,400 lb./sq. in. by injection of ethylene, and the heating was continued. The reaction mixture was maintained at 95°C, and the pressure in the range 1,200–1,400 lb./sq. in. by injection of additional ethylene as required, for 5 h. The reaction product was then removed from the cooled reactor, separated from the water, and dried over anhydrous magnesium sulfate. After removal of the unreacted carbon tetrachloride by distillation, a preliminary fractional distillation gave the following results:
The pure compounds can be obtained from these cuts by redistillation.
1,3,3,5,7,7,9-Heptachlorononane (Fig. 40) 
A mixture of 2.8 moles of 1,1,1,3-Tetrachloropropane, 2.8 moles of allyl chloride, 350 mL of i-C3H7OH, and 49 mmoles of Fe(CO)5 was heated in an 0.5-L steel autoclave for 2 h at 135°C. The reaction products were washed with 15% HCl solution, extracted with CHCl3, dried over MgSO4, and fractionally distilled. The following fractions were obtained: (I) b.p. 51–65°C (30 mm), 206.8 g; (II) b.p. 78–100°C (30 mm), 11 g; (III) b.p. 42–56°C (3 mm), 15.2 g; (IV) b.p. 79–93°C (1 mm), 29.7 g; (V) b.p. 92–101°C (0.9 mm), 172 g. The residue weighed 54.5 g. Based on the GLC analysis, fraction I contained 1.2 moles of pure 1,1,1,3-Tetrachloropropane (57%conversion). Fractions II and III respectively contained 90 and 70% of 4,4,6-trichloro-l-hexene. The pure 4,4,6-trichloro-l-hexene was isolated from fraction II by preparative GLC. Fractions IV and V respectively contained 35 and 80% of 1,2,4,4,6-pentachlorohexane (36% when based on reacted 1,1,1,3-Tetrachloropropane). GLC analysis on two phases of different polarity disclosed that fraction IV also contained 1,3,3,5-tetrachlorohexane. Fraction V was treated with conc. H2SO4 to remove the by-products that were formed by the alkoxylation of the allylic Cl atom, washed with water, dried over MgSO4, and repeatedly distilled to give the pure 1,2,4,4,6-pentachlorohexane. The residue (54.5 g) was extracted with petroleum ether. Distillation of the extract gave a fraction with b.p. 150–153°C (0.8 mm), which, based on the GLC analysis and NMR spectral data, contains 95% of 1,3,3,5,7,7,9-heptachlorononane (ClCH2CH2CCl2CH2)2CHCl.
1,10-Dichlorodecane (Fig. 47a) 
A mixture of 100 g of 1,5,5,6,6,10-hexachlorodecane, 100 g of diethylamine, 200 mL of ethanol, and 12 g of Raney nickel was placed in a 1-L rotating autoclave. Hydrogen was passed into the autoclave until the pressure attained 100 atm. The reaction was carried out at 50–55°C, hydrogen being passed in as necessary so that the pressure was maintained at 100–120 atm. After 8 h, reaction ceased. The products obtained were 41 g (68%) of 1,10-dichlorodecane (b.p. 105–106°C (1.5 mm) and 15 g (19%) of 1,5,6,10-tetrachlorodecene-5.
1,2,5,6-Tetrachlorodecane and 1,1,1,3,10,12,12,12-Octachlorododecene (Figs. 4 and 5) 
Hydrogenation of the compounds 5,6,9,10-tetrachlorodecenes-1, 1,2,5,9,10-pentachlorodecene-5, 1,1,1,3,10,12,12,12-octachlorododecenes-6: 0.5 g of 5,6,9, 10-tetrachlorodecenes-1 (or 1,2,5,9,10-pentachlorodecene-5, 1,1,1,3,10,12,12, 12-octachlorododecenes-6) was dissolved in 50 mL of ethylacetate in a round-bottom flask with two necks, and 50 mg Pd on activated carbon was added. Hydrogenation of the magnetically stirred sample was carried out under about 5 psi H2 of overpressure. After completion of the reaction, the solution was filtered, the solvent rotary evaporated and redissolved in petroleum ether. Contrary to 5,6,9,10-tetrachlorodecenes-1, and 1,2,5,9,10-pentachlorodecene-5, the hydrogenation products of 1,1,1,3,10,12,12,12-octachlorododecenes-6 were identical, and could be isolated only in about 50% purity after threefold chromatography on silica gel column (100 × 2.6 cm). Therefore, these samples were further chromatographed on a GPC column with hexane–dichloromethane (1:1). Finally, purification on silica gel was again necessary to obtain the product with a purity of more than 90%.
1,2,9,10-Tetrachlorodecane (Fig. 2) 
1,2,9,10-Tetrachlorodecane was synthesized by chlorine addition to 1,9-decadiene using a variation of the procedure reported by Tomy . Approximately 10 mL of 0.05 M NaOH was layered over 40 mL of dichloromethane in a round bottom flask. Chlorine gas was gently bubbled through the DCM layer for several minutes before introduction of 1,9-decadiene into the lower DCM layer by pipette. After a brief reaction period, the layers were separated and the DCM layer was analyzed by GC/MS. The total ion chromatogram produced one dominant peak with a retention time of 13.7 min and an EI mass spectrum confirming the identity of the product as tetrachlorodecane. The very small amounts of higher chlorinated decane isomers (with chlorine number > 4) evident in the chromatogram indicated that free radical substitution reactions were minimal.
1,3,3,5-Tetrachlorodecane, 1,3,3,5-Tetrachlorononane and 1,3,5-Trichlorodecane (Fig. 25) 
1,3,3,5-Tetrachlorodecane was obtained similarly to 1,3,3,5-tetrachlorononane from 250 mmoles of l-heptene, 750 mmoles of 1,1,1,3-tetrachloropropane, 25 mmoles of Fe(CO)5, and 100 mmoles of DMF at 105°C in the course of 3 h. The yield of 1,3,3,5-Tetrachlorodecane was 52%, b.p. 117°C (2 mm). 13C NMR spectrum (δ, ppm): 38.8 (C-1) 49.8 (C-2), 89 9 (C-3), 56.5 (C-4), 57.8 (C-5), 39.4 (C-6), 31.0 (C-7), 25.5 (C-8), 22.3 (C-9), 13.8 (C-10).
Reduction of 1,3,3,5-tetrachloroalkanes was carried out in sealed glass ampoules (140°C, 3 h, with rotary stirring). 1,3,5-Trichlorodecane was obtained from 25 mmoles of 1,3,3,5-Tetrachlorodecane. The mixture was passed through a layer (30 mm) of silica gel L 100/160, and the silica gel was washed with 20 mL of CCl4. After distillation of low-boiling products, the mixture was distilled in vacuo; 1,3,5-Trichlorodecane was isolated, yield 84%, b.p. 114°C (2 mm), 13C NMR spectrum (δ, ppm): 40.3 (C-1), 40.9 (C-2), 56.4 (C-3), 46.9 (C-4), 58.8 (C-5), 37.9 (C-6), 31.1 (C-7), 25.7 (C-8), 22.5 (C-9), 13.9 (C-10).
2,5,6,9-Tetrachlorodecane and 1,2,5,6,9-Pentachlorodecane (Fig. 4) 
0.5 g of 5,6-dichlorodecadienes-1,9 or 5,6,9,10-tetrachlorodecenes-1 and 100 µl SnCl4 were dissolved in 15 mL of water-free dioxan in a 20 mL headspace vial. HCl gas generated from conc. hydrochloric acid by heating in a round-bottom flask and dried over CaCl2 was introduced into the dioxan solution up to saturation. After this, the sealed vial was kept in an oven at 60°C for about 2 days. The course of the reaction was followed gas chromatographically by injection of samples taken every 16 h with a GC syringe. The products were extracted from dioxan with petroleum ether after the addition of water. For the purification, a silica gel column (100 × 2.6 cm) with petroleum ether as eluent was used.
1,1,1,3,9,10-Hexachlorodecane, 1,1,1,3,6,7,10,11-Octachloroundecane, 1,1,1,3,6,7,10,12,12,12-Octachlorododecane (Fig. 5) 
Chlorination of the compounds 9,11,11,11-tetrachloroundecadienes-1,5 and 1,1,1, 3,10,12,12,12-octachlorodecenes-6, 8,10,10,10-tetrachlorodecene-1 and 9,11,11, 11-tetrachloroundecene-1. 300 mg of the compound was dissolved in 25 mL of CCl4, to which 250 mg chlorine in 5 mL CCl4 was added under exclusion of light. From 9,11,11,11-tetrachloroundecadienes-1,5, first hexachloroundecenes were formed, which were not isolated and the reaction was continued to 1,1,1, 3,6,7,10,11-octachloroundecane.
Chlorination of 1,1,1,3,10,12,12,12-octachlorodecenes-6 yielded 1,1,1,3,6,7,10, 12,12,12-octachlorododecane, and that of 8,10,10,10-tetrachlorodecene-1 yielded the product 1,1,1,3,9,10-hexachlorodecane. By the same method, compound 1,1,1,3,10,11-hexachloroundecane was obtained from 9,11,11,11-tetrachloroundecene-1. The purification of all end products was carried out on silica gel column with petroleum ether as described above.
1,2,5,6,9,10-Hexachlorodecane (Fig. 4) 
Chlorination of 1,5,9-decatriene: 1.75 g chlorine dissolved in 100 mL of CCl4 was slowly dropped into an intensively magnetically stirred solution of 2.5 g 1,5,9-decatriene in 50 mL of CCl4 at 0°C. Another reaction charge was carried out under the same reaction conditions with 2.5 g 1,5,9-decatriene and 3.5 g chlorine. After completion of the reaction of chlorine, the two solutions were pooled and the solvent was rotary evaporated. The crude product was chromatographed on a column (100 cm × 5.5 cm i.d.) of silica gel with petroleum ether as eluent. The compounds 5,6-dichlorodecadiene-1,9, 5,6,9,10-tetrachlorodecene-1 and 1,2,5, 6,9,10-hexachlorodecane were eluted successively. If necessary, the chromatography was repeated to reach a purity of more than 95%.
Synthesis of the compounds 9,11,11,11-tetrachloroundecadienes-1,5 and 1,1,1, 3,10,12,12,12-octachlorodecenes-6: 15 g 1,5,9-decatriene were refluxed in 150 mL CCl4 for 6 days, adding 0.5 g AIBN every day during refluxing. After that, the reaction solution was treated with 100 mL of conc. sulfuric acid. The organic phase was separated, washed with water, and rotary evaporated. The residue was dissolved in 50 mL petroleum ether and fractionated over a short silica gel column (50 cm × 5 cm) to separate 9,11,11,11-tetrachloroundecadienes-1,5 from 1,1,1,3,10,12,12,12-octachlorodecenes-6. Thereafter, both compound mixtures were chromatographed with petroleum ether again on silica gel column (100 cm × 2.6 cm), whereas for the separation of 1,1,1,3,10,12,12,12-octachlorodecenes-6, silica gel was activated before use at 150°C for 24 h.
1,2,5,6,9,10-Hexachlorodecane (Fig. 1) 
1,2,5,6,9,10-Hexachlorodecane was synthesized by bubbling chlorine gas, at room temperature, into neat 1,5,9-decatriene (Aldrich Chemical Co.) contained in a flask wrapped in aluminum foil to exclude light. The desired compound was the major product of the reaction, as verified by analysis of a 10% solution of the product mixture in hexane by HRGC/MS. In an attempt to prepare an analytical standard, we treated the reaction products as follows. To remove unreacted alkenes, the product mixture (0.25 mL) was mixed with 2 mL of H2SO4/HNO3 (1:1) at 70°C for 20 min and then cooled in an ice bath. After distilled water (5 mL) had been added, the mixture was extracted with hexane (3 × 3 mL). The combined extracts were concentrated to 1 mL and chromatographed on a Florisil column, as described below. Analysis by GC/MS (positive ion TIC) showed the major products to be C10H16Cl6, C10H15Cl7, C10H14Cl8, and C10H13Cl9. Additional peaks in the chromatogram accounted for 7 ± 2% of the TIC.
1,5,5,6,6,10-Hexachlorodecane, A (Fig. 47a) 
1,1,1,5-Tetrachloropentane (500 g) and 794 mL of a solution of ammonia in ethanol containing 50 g of ammonia were added to previously reduced platinum oxide (2.38 g of platinum oxide in 320 mL of alcohol and 10 mL of glacial acetic acid). Reduction was carried out at atmospheric pressure; it proceeded with evolution of heat. In the course of 9 h, 35 L of hydrogen was absorbed. The reaction mixture was diluted with water until the ammonium chloride was dissolved, and it was then filtered. The precipitate of 1,5,5,6,6,10-hexachlorodecane was dissolved in chloroform, and the solution was dried over calcium chloride. The solvent was removed, and low-boiling substances (180 g) were removed under reduced pressure, The hexachlorodecane, which remained behind, was recrystallized from alcohol. The product was 202 g (48.5%) of hexachlorodecane, m.p. 84–85°C.
1,5,5,6,6,10-Hexachlorodecane, B (Fig. 47d) 
To a solution of 100 g tetrachloropentane in 50 mL ether was added a solution of ethylmagnesium bromide (from 68 g ethyl bromide and 15 g magnesium) m 125 mL ether at such a rate that the ether boiled moderately. Gas consisting of ethane and ethylene was evolved. The mixture was heated and boiled for 15 mm and treated as in the previous experiment (see 5.1.25). Vacuum distillation gave 59.5 g of a fraction with b.p. 78–93°C (9 mm) and 21.4g residue.
Column fractionation gave 44.3 g 1,1,5-trichloropentane with b.p. 82–84°C (8 mm) and 12.4g of the original tetrachloropentane. From the residue was isolated 15.1 g 1,5,5,6,6,10-hexachlorodecane with m.p. 83–84°C and 3.8 g of 1,5,6,10-tetrachlorodecene-5 with b.p. 150–152°C (2.5 mm).
To a solution of 40 g 1,1,1,5-tetrachloropentane m 30 mL ether and 2 g anhydrous cobalt chloride was added with mixing ethylmagnesium bromide (from 26 g ethyl bromide and 6 g magnesium) m 70 mL ether. After treatment of the mixture as in the previous experiment, 8.4 g of 1,5,5,6,6,10-hexachlorodecane, 2.3 g of 1,5,6,10-tetrachlorodecene, 12.4 g 1,1,5-trichloropentane, and 5 g of the original tetrachloropentane were obtained.
1,1,1,3,8,10,10,10-Octachlorodecane, 1,1,1,3,9,11,11,11-Octachloroundecane, 1,1,1,3,10,12,12,12-Octachlorododecane (Fig. 5) 
The synthesis of 1,1,1,3,10,12,12,12-octachlorododecane and 9,11,11,11-tetrachloroundecene-1 (from 1,9-decadiene), 1,1,1,3,8,10,10,10-octachlorodecane (from 1,7-octadiene), and 8,10,10,10-tetrachlorodecene-1 and 1,1,1,3,9,11,11,11-octachloroundecane (from 1,8-nonadiene) was analogous with the above-described synthesis of 1,2,5,6,9,10-hexachlorodecane (see 5.1.23). Separation of diastereomers could not be achieved under the experimental conditions used. The products were purified on a silica gel column (100 cm × 2.6 cm) with petroleum ether.
1,1-Dichloroundecane, 1,1,5-Trichloroundecanes and 1,1,6-Trichloroundecanes (Figs. 42 and 43) 
The reaction product from 1,1,1-trichloroundecane (9.5 g, 40 mmole) was fractionated in vacuum. Fractions obtained were: 1) b.p. 68–70°C (1.5 mm) (1.7 g); 2) b.p. 80–85°C (1 mm) (3.1 g); 3) b.p. 85–89°C (1 mm) (4 g).
From fraction 1, consisting of 95% 1,1-dichloroundecane and 5% 1,1,1-trichloroundecane according to GLC data, a repeat distillation gave 1,1-dichloroundecane b.p. 98°C (1.5 mm). 13C NMR spectrum (δ, ppm): 73.2 (C-1), 43.7 (C-2), 30.1 (C-3), 26.3 (C-4), 29.0 (C-5), 29.3 (C-6), 29.5 (C-7), 26.0 (C-8), 31.9 (C-9), 22.6 (C-10), 13.9 (C-11).
According to GLC, fraction 3 contained 80% 1,1,5- and 1,1,6-trichloroundecane and 20% other isomers.
1,7,7,8,8,14-Hexachlorotetradecane (Fig. 47a) 
1,1,1,7-Tetrachloroheptane (83 g) and a solution of 8 g of ammonia m 80 mL of methanol were added to previously reduced 5% Pd/BaSO4 (2 g) in 25 mL of methanol and 1 mL of glacial acetic acid. During the hydrogenation the reaction mixture became warm. After 3 h, when 6.1 L of hydrogen had been absorbed, the absorption of hydrogen ceased. The methanolic solution was filtered from the catalyst and ammonium chloride, and the precipitate was washed with chloroform on the filter. Water was added to the filtrate. The chloroform layer was dried over calcium chloride. After removal of chloroform under reduced pressure the low-boiling products were distilled off (28 g). Recrystallization of the residue from ethanol yielded 32.1 g (45.5%) of 1,7,7,8,8,14-hexachlorotetradecane, m.p. 57–58°C.
1,14-Dichlorotetradecane (Fig. 47a) 
Tetrachloroheptane (90 g) was hydrogenated in the presence of 1.5 g of Pd/BaSO4 and 8.1 g of ammonia in 100 mL of methanol for 2 h 30 min, in the course of which 7.5 L of hydrogen was absorbed. The Catalyst and ammonium chloride were filtered off, methanol was distilled off, and low-boiling fractions were removed under reduced pressure. The residue (42 g) was hydrogenated in the presence of 3 g of Pd/BaSO4 and 32 g of diethylamine in 80 mL of ethanol for ten hours. The product was 14.5 g (28%) of 1,14-dichlorotetradecane, b.p. 144–146°C (1.8 mm), together with about 8 g of a mixture boiling at 180–180°C (1 mm) and consisting mainly of tetrachlorotetradecene.
1,1,14,14-Tetrachlorotetradecane (Fig. 47d) 
With stirring, to 1.0 g of Mg, activated with iodine, was added a mixture of 9.9 g of 1,1-dichloro-7-bromoheptane and 0.9 g of 1,2-dibromoethane in 80 mL of absolute ether. The reaction started immediately. After heating the mixture for 3 h, followed by the usual workup and vacuum-distillation, we obtained 0.9 g of 1,1-dichloroheptane, 2.9 g of the starting bromide, and 2.7 g of 1,1,14,14-tetrachlorotetradecane with b.p. 171–174°C (<1 mm). The latter after redistillation had b.p. 156–158°C (0.5 mm).
1,9,9,10,10,18-Hexachlorooctadecane (Fig. 47a) 
A solution of 6.8 g (0.4 mole) of ammonia in 110 mL of methanol and 106 g (0.4 mole) of 1,1,1,9-tetrachlorononane were added to previously reduced palladium oxide (6 g of 5% Pd/BaSO4 in 50 mL of methanol containing 2 mL of glacial acetic acid. The hydrogenation was carried out in a glass hydrogenation flask at atmospheric pressure. After ten hours the absorption of hydrogen stopped. In all, 4.5 L of hydrogen was absorbed. The catalyst was filtered off and washed with water and chloroform; the chloroform layer was dried over calcium chloride. After distillation of the chloroform we obtained 47.5 g (51.7%) of 1,9,9,10,10,18-hexachlorooctadecane, m. p. 55.5–56°C (from a mixture of alcohol and acetone). In addition we isolated 10 g of nonyl chloride; b.p. 55–56°C (1 mm).
Typical Reaction Conditions for the Ru-Catalyzed Addition of Haloalkanes to oct-1-ene (Fig. 32) 
Oct-1-ene (3.4 g, 0.03 mol), haloalkane (0.06 mol) and [RuCl2(PPh3)3] (0.01 g, 1 × 10−5 mol) were loaded into a glass tube with a restriction in the neck to facilitate sealing. The reaction mixture was degassed three times by the freeze-pump-thaw method and the tube was then sealed under vacuum. The tube was then heated to the desired temperature in an oven for times varying between 1.5 and 20 h, after which time it was opened and the contents analyzed by GLC.