Macrocycle-supported titanium complexes with chelating imido ligands: analogues of ansa-metallocenes.

Reactions of 1,4-dimethyl-1,4,7-triazacyclononane (L1a) and 1,4-diisopropyl-1,4,7-triazacyclononane (L1b) to form 1-aminopropyl-4,7-di-R-1,4,7-triazacyclononane [R = Me (H2L3a) or Pri (H2L3b)] and 1-(2-aminobenzyl)-4,7-di-R-1,4,7-triazacyclononane [R = Me (H2L5a) or Pri (H2L5b)] are reported. Reaction of H2L3a and H2L5a with [Ti(NMe2)2Cl2] gives the ansa-linked macrocycle-imido complexes [Ti(kappa 4-L3a)Cl2] (5a) and [Ti(kappa 4-L5a)Cl2] (6a), respectively, and NHMe2. Reaction of H2L3a with [Ti(NBut)Cl2(py)3] gives [Ti(NBut)(kappa 3-H2L3a)Cl2] (7), which possesses a pendant alkylamine group that does not undergo amine/tert-butylimido group exchange to give 5a and ButNH2. However, reaction of H2L3b and H2L5b with [Ti(NBut)Cl2(py)3] does give amine/tert-butylimido group exchange to form [Ti(kappa 4-L3b)Cl2] (5b), [Ti(kappa 4-L5b)Cl2] (8b), and ButNH2. The compounds 5a,b and 6a,b are isolobal analogues of group 4 ansa-metallocene complexes and relatives of titanium cyclopentadienyl-amido constrained geometry olefin polymerization catalysts. Reaction of 5b with AgOTf affords [Ti(kappa 4-L3b)(OTf)Cl] (8) as the major product, the crystal structure of which has been determined. Alkylation of 6b by RLi gives the dialkyl derivatives [Ti(kappa 4-L5b)(R)2] [R = Me (9) or CH2SiMe3 (10)]. The ethylene polymerization capability of the compounds 5a,b, 6a,b, and 10 in the presence of methylaluminoxane has been determined and compared to that of [Ti(NBut)(kappa 3-L1a,b)Cl2] (11a,b); in all instances, low yields of high-molecular-weight polymer are obtained.

Risk factors associated with oesophageal cancer in Bulawayo, Zimbabwe.

This report presents information on risk factors for oesophageal cancer in Bulawayo, Zimbabwe. The data analysed were from the Cancer Registry of Bulawayo for the years 1963-77, when all registered patients were interviewed using a standard questionnaire. The age-standardised incidence rates in the urban population of Bulawayo in the first 10 year period were 58.6 per 100,000 in men and 8.1 in women. The distribution of risk factors was assessed in 881 oesophageal cancer cases (826 male, 55 female) and a control group comprising other non-tobacco- and non-alcohol-related cancer (5238) cases. There was a marked geographical gradient in risk in both sexes, which remained after adjustment for lifestyle variables. In men tobacco smoking was significantly associated with risk of oesophageal cancer, with the relative risk rising to 5.7 among smokers of 15 or more g day-1; this effect is independent of alcohol drinking. Among women who had ever smoked tobacco, the relative risk was 4.0 compared with those who had never smoked. Alcohol intake showed no independent effect on risk. Low socioeconomic status [odds ratio (OR) = 1.5; confidence interval (CI) = 1.0-2.1] and working as a miner (OR = 2.5; CI = 1.5-4.2) conferred increased risks in comparison with men of high socioeconomic status.

Bladder cancer: epidemiology and risk factors in Bulawayo, Zimbabwe.

The incidence of bladder cancer, and the importance of some selected risk factors in its etiology, were estimated from the data collected in the cancer registry of Bulawayo, Zimbabwe, during the period 1963-77. Cancer cases were interviewed with a standard questionnaire, and more than 70 percent of these were complete. Incidence rates in the urban population of Bulawayo in the first 10-year period were relatively high, with age standardized rates of 17.9 per 100,000 in men and 9.5 in women. Risk-factor distribution was compared in 680 bladder cancer cases (494 males, 186 females) and a control group comprising other cases with non-tobacco-related cancers (8,201). Seventy-one percent of bladder cancer cases were squamous cell carcinomas. The presence of schistosomiasis, evaluated from past history of bilharzia or hematuria, was associated with a significantly increased risk of bladder cancer in both genders (odds ratio [OR] = 3.9 for men, 5.7 for women), a result reflected in the differing risk by province of residence, which correlated with the prevalence of infection among cancer cases. The proportion of bladder cancer attributable to schistosomiasis was estimated to be 28 percent. Social status, as reflected by education level, also influenced risk (ORs for literate cf illiterate males = 0.6), but tobacco smoking in men had no effect on the risk of squamous cell tumors. For transitional cell carcinomas or adenocarcinomas, there was a nonsignificant increased risk of 2.0 in the highest smoking categories (15 g of tobacco per day), compared with non smokers.

Cancer patterns and risk factors in the African population of southwestern Zimbabwe, 1963-1977.

The incidence of cancer and the importance of some selected risk factors in its etiology were estimated from the data collected in the cancer registry of Bulawayo, Zimbabwe, during the period 1963-1977. Cancer cases were interviewed with a standard questionnaire, and more than 71% of these were complete. In men, the most frequent cancer sites were liver, esophagus, and lung, while in women, cervical cancer was the dominant malignant tumor, followed by cancers of the liver, breast, and bladder. Risk factors of cancer cases were estimated by case-control analysis in which other cancers (excluding tobacco-related cancers in men and hormone-related cancers in women) were considered as controls. In men, tobacco smoking was associated with increased risk of lung cancer (odds ratio OR2, 5.2) and esophagus cancer (OR, 5.6) in the highest consumption category (15 g of tobacco per day) compared to nonsmokers. Copper (OR, 1.5), gold (OR, 1.5), and nickel (OR, 2.6) miners had an increased risk of lung cancer, but no increase was found among asbestos miners (OR, 0.7). There was no independent effect of alcohol consumption on the risk of esophagus cancer. The presence of schistosomiasis was associated with a significantly increased risk of bladder cancer (OR, 3.9). The risk of invasive cervical cancer increased with number of children--the estimated odds ratio was 1.8 in women with six or more births--but no consistent association was found for first intercourse. In postmenopausal women, the risk of breast cancer increased with age at first pregnancy (but not in the highly fertile) and decreased with high parity, if age at first pregnancy was 19 or more.